CN114072379B - Method for producing actinic-ray-or radiation-sensitive resin composition, method for forming pattern, and method for producing electronic device - Google Patents

Method for producing actinic-ray-or radiation-sensitive resin composition, method for forming pattern, and method for producing electronic device Download PDF

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CN114072379B
CN114072379B CN202080045638.0A CN202080045638A CN114072379B CN 114072379 B CN114072379 B CN 114072379B CN 202080045638 A CN202080045638 A CN 202080045638A CN 114072379 B CN114072379 B CN 114072379B
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acid
solvent
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solution
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CN114072379A (en
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王惠瑜
丹吴直纮
山本庆
丸茂和博
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Fujifilm Corp
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    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
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Abstract

The invention provides a method for producing a actinic-ray-sensitive or radiation-sensitive resin composition capable of forming a pattern with suppressed defects. Another object of the present invention is to provide a pattern forming method including the method for producing a actinic-radiation-sensitive or radiation-sensitive resin composition, and a method for producing an electronic device using the pattern forming method. The method for producing a actinic-ray-or radiation-sensitive resin composition of the present invention is a method for producing a actinic-ray-or radiation-sensitive resin composition comprising at least a resin having an increased polarity by decomposition by the action of an acid, a compound which generates an acid by irradiation with actinic rays or radiation, and a solvent, wherein the compound which generates an acid by irradiation with actinic rays or radiation comprises 1 or more compounds selected from the group consisting of compounds (I) to (III), and the 1 st solution comprising the resin having an increased polarity by decomposition by the action of an acid and the 1 st solvent is mixed with 1 or more compounds selected from the group consisting of compounds (I) to (III).

Description

Method for producing actinic-ray-or radiation-sensitive resin composition, method for forming pattern, and method for producing electronic device
Technical Field
The present invention relates to a method for producing a actinic-ray-sensitive or radiation-sensitive resin composition, a method for forming a pattern, and a method for producing an electronic device.
Background
In order to compensate for the decrease in sensitivity due to light absorption after a resist for KrF excimer laser (248 nm), a pattern formation method using chemical amplification is used. For example, in the positive type chemical amplification method, first, a photoacid generator contained in an exposure portion is decomposed by light irradiation to generate an acid. Then, in a baking process after exposure (PEB: post Exposure Bake) or the like, the alkali-insoluble group of the resin contained in the actinic ray-sensitive or radiation-sensitive resin composition (hereinafter, also referred to as "resist composition") is changed to an alkali-soluble group or the like by the catalytic action of the generated acid, whereby the solubility to the developer is changed. After that, development is performed, for example, using an alkaline aqueous solution. Thus, the exposure portion is removed to obtain a desired pattern.
In order to miniaturize semiconductor devices, the shorter wavelength of exposure light sources and the higher numerical aperture (higher NA) of projection lenses have been advanced, and exposure machines using ArF excimer lasers having a wavelength of 193nm as light sources have been developed.
Under such circumstances, various structures have been proposed as a actinic ray-sensitive or radiation-sensitive resin composition.
For example, patent document 1 discloses an acid generator containing a salt represented by the following formula (I) as a component used in a resist composition.
[ chemical formula 1]
Technical literature of the prior art
Patent literature
Patent document 1: japanese patent laid-open No. 2015-024989
Disclosure of Invention
Technical problem to be solved by the invention
The present inventors have studied the resist composition described in patent document 1, and as a result, have found that when a pattern is formed using the resist composition, many defects occur in the pattern. That is, it is clear that further improvement of the above-mentioned resist composition is required to suppress defects of the formed pattern.
Accordingly, an object of the present invention is to provide a method for producing a actinic-ray-or radiation-sensitive resin composition capable of forming a pattern with suppressed defects.
The present invention also provides a pattern forming method including the method for producing a actinic-radiation-sensitive or radiation-sensitive resin composition, and a method for producing an electronic device using the pattern forming method.
Means for solving the technical problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, they have completed the present invention. That is, it has been found that the above problems can be solved by the following constitution.
[ 1 ] A method for producing a actinic-ray-or radiation-sensitive resin composition comprising at least a resin which is decomposed by the action of an acid and has an increased polarity, a compound which generates an acid by irradiation with actinic rays or radiation, and a solvent,
in the method for producing a actinic-ray-or radiation-sensitive resin composition, the compound that generates an acid upon irradiation with actinic rays or radiation contains 1 or more compounds selected from the group consisting of compounds (I) to (III) described later,
a actinic-ray-or radiation-sensitive resin composition is produced by mixing a 1 st solution containing the resin having an increased polarity by decomposition with an acid and a 1 st solvent with 1 or more compounds selected from the group consisting of the compounds (I) to (III).
The method for producing a actinic-ray-or radiation-sensitive resin composition according to [ 1 ], wherein,
The SP value of the 1 st solvent is less than 18.5MPa 1/2 。
The method for producing a actinic-ray-or radiation-sensitive resin composition according to [ 1 ] or [ 2 ], wherein,
the 1 st solution and the 2 nd solution are mixed to produce a actinic ray-or radiation-sensitive resin composition, wherein the 2 nd solution contains a 2 nd solvent having a larger SP value than the 1 st solvent and at least one compound selected from the group consisting of the compounds (I) to (III).
The method for producing a actinic-ray-or radiation-sensitive resin composition according to [ 3 ], wherein,
the SP value of the 2 nd solvent is 18.5MPa 1/2 The above.
The method for producing a actinic-ray-or radiation-sensitive resin composition according to [ 3 ] or [ 4 ], wherein,
the concentration of the solid content in the solution 1 is 5.0 to 20.0 mass%,
the 1 st solvent is further mixed with the 3 rd solution obtained by mixing the 1 st solution and the 2 nd solution to produce a actinic-ray-or radiation-sensitive resin composition.
[ 6 ] A pattern forming method comprising the steps of:
a step of forming a resist film on a support using the actinic-ray-or radiation-sensitive resin composition obtained by the process for producing an actinic-ray-or radiation-sensitive resin composition according to any one of [ 1 ] to [ 5 ];
Exposing the resist film; and
and developing the exposed resist film with a developer.
[ 7 ] A method for producing an electronic device, comprising the pattern forming method described in [ 6 ].
Effects of the invention
According to the present invention, a method for producing a actinic-ray-or radiation-sensitive resin composition capable of forming a pattern with suppressed defects can be provided.
Further, according to the present invention, a pattern formation method including the above-described method for producing a actinic-radiation-sensitive or radiation-sensitive resin composition, and a method for producing an electronic device using the above-described pattern formation method can be provided.
Drawings
Fig. 1 is a schematic diagram for explaining an evaluation method of defect evaluation after pattern formation, and is an example of the observed defect.
Fig. 2 is a schematic diagram for explaining an evaluation method of defect evaluation after pattern formation, and is another example of the observed defect.
Detailed Description
Hereinafter, a method for producing a actinic-ray-sensitive or radiation-sensitive resin composition, a method for forming a pattern, and a method for producing an electronic device according to the present invention will be described in detail.
The constituent elements described below can be described according to the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the labeling of groups (atomic groups) in the present specification, unless contrary to the gist of the present invention, unsubstituted and substituted labels are described to include groups having substituents in addition to groups having no substituents. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present specification, the term "organic group" means a group containing at least one carbon atom.
The substituents are preferably 1-valent substituents, unless otherwise indicated.
The term "actinic rays" or "radiation" in the present specification means, for example, an open line spectrum of a mercury lamp, extreme ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light: extreme Ultraviolet), X-rays, electron beams (EB: electron Beam), and the like. The term "light" in this specification means actinic rays or radiation.
Unless otherwise indicated, "exposure" in the present specification includes not only exposure by an open line spectrum using a mercury lamp, extreme ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and the like, but also drawing by a particle beam such as an electron beam and an ion beam.
In the present specification, "to" is used to indicate the meaning of including the numerical values described before and after the "to the" as the lower limit value and the upper limit value.
The bonding direction of the 2-valent group labeled in this specification is not limited unless otherwise specified. For example, when Y in the compound represented by the general formula "X-Y-Z" is-COO-, Y may be-CO-O-, or-O-CO-. And the above-mentioned compound may be "X-CO-O-Z", or "X-O-CO-Z".
In the present specification, (meth) acrylate means acrylate and methacrylate, and (meth) acrylic acid means acrylic acid and methacrylic acid.
In the present specification, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the dispersity (also referred to as molecular weight distribution) (Mw/Mn) of the resin are defined as polystyrene-converted values by GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection amount): 10. Mu.L, column (column): TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40 ℃, flow rate: 1.0 mL/min, detector: differential refractive index detector (Refractive Index Detector)) using a GPC (Gel Permeation Chromatography ) apparatus (HLC-8120 GPC manufactured by TOSOH CORPORATION).
In the present specification, the acid dissociation constant (pKa) means an acid dissociation constant (pKa) in an aqueous solution, and specifically, a value of a database based on a substituent constant of hamett (Hammett) and a known literature value is calculated using the following software package 1. The values of the acid dissociation constants (pKa) described in the present specification all represent values obtained by calculation using the software package.
Software package 1: advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).
On the other hand, the acid dissociation constant (pKa) can also be determined by a molecular orbital algorithm. As a specific method, there may be mentioned a method of calculating H in an aqueous solution based on a thermodynamic cycle + A method for calculating the dissociation free energy. Concerning H + The method of calculating the dissociation free energy may be calculated by DFT (density functional method), for example, but other various methods have been reported in literature and the like, and are not limited thereto. In addition, there are a plurality of software capable of implementing DFT, for example, gaussian16.
As described above, the acid dissociation constant (pKa) in the present specification is a value obtained by calculating a value of a database based on a substituent constant of hamite and a known literature value using the software package 1, but when the acid dissociation constant (pKa) cannot be calculated by this method, a value obtained by Gaussian16 based on DFT (density functional method) is used.
As described above, the acid dissociation constant (pKa) in the present specification refers to "acid dissociation constant (pKa) in an aqueous solution", but when the acid dissociation constant (pKa) in an aqueous solution cannot be calculated, "acid dissociation constant (pKa) in a dimethyl sulfoxide (DMSO) solution" is used.
In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
[ method for producing actinic-ray-sensitive or radiation-sensitive resin composition ]
The method for producing a actinic-ray-or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "the method for producing the present invention") relates to a method for producing a actinic-ray-or radiation-sensitive resin composition (hereinafter also referred to as "the resist composition") which comprises at least a resin (hereinafter also referred to as "acid-decomposable resin" or "resin (a)") which is decomposed by the action of an acid and has an increased polarity, a compound which generates an acid by irradiation of actinic rays or radiation (hereinafter also referred to as "photoacid generator"), and a solvent.
The 1 st feature of the production method of the present invention is that the photoacid generator contains 1 or more photoacid generators (hereinafter also referred to as "specific photoacid generators") selected from the group consisting of the compounds (I) to (III) described below. In addition, as the 2 nd characteristic point of the production method of the present invention, there is mentioned a point that when producing a resist composition, first, a 1 st solution containing an acid-decomposable resin and a 1 st solvent is prepared, and a specific photoacid generator is mixed with the 1 st solution.
In this time, the present inventors have clarified that photoacid generators having a multivalent (e.g., 2-valent) salt structure in the molecule, such as the photoacid generator represented by the above general formula (I) used in patent document 1, are likely to aggregate with each other due to the above salt structure in the resist composition, and as a result, many defects occur in forming a pattern.
As a result of intensive studies on the above findings, the present inventors have found that a method for producing a resist composition by preparing a polymer solution (solution 1) containing an acid-decomposable resin and a solvent (solution 1) in advance, and mixing a specific photoacid generator, which is a photoacid generator having a multivalent salt structure in the molecule, with the polymer solution (solution 1) can suppress defects in the formed pattern.
Although the mechanism of action is not clear, it is presumed that, when a specific photoacid generator is mixed with a polymer solution containing an acid-decomposable resin and a solvent, the solubility of the specific photoacid generator in the solvent is improved by the action of the acid-decomposable resin, and as a result, the formation of aggregates between the specific photoacid generators is suppressed. This is also apparent from the example columns of this specification. That is, as can be seen from the following, for example, referring to tables 1 and 6, in comparative example 1 in which a resist composition was prepared by directly mixing an acid-decomposable resin, a specific photoacid generator, and a solvent, and comparative example 2 in which a resist composition was prepared by directly mixing a solution in which a specific photoacid generator was dissolved in a solvent in advance, with an acid-decomposable resin, the desired results were not obtained in terms of defect suppression.
As will be described later, it was confirmed that the defect suppression performance of the formed pattern was further excellent by the method of preparing a resist composition by previously preparing a solution (solution 2) obtained by dissolving a specific photoacid generator in a solvent (solution 2) having a larger SP value than the above-mentioned solvent 1 and mixing the solution 2 with the above-mentioned solution 1.
As will be described later, it was confirmed that the defect suppression performance of the formed pattern was further excellent in the manufacturing method of preparing the resist composition by further mixing the 1 st solvent contained in the 1 st solution with the 3 rd solution obtained by mixing the 1 st solution with the 2 nd solution, based on the solid content concentration of the 1 st solution being 5.0 to 20.0 mass%.
Further, as will be described later, it was confirmed that the SP value of the 1 st solvent contained in the 1 st solution was set to be less than 18.5MPa 1/2 The SP value of the 2 nd solvent contained in the 2 nd solution was set to 18.5MPa 1/2 In the above method for producing a resist composition, the defect suppressing performance of the formed pattern is more excellent.
The resist composition that can be produced by the production method of the present invention will be described below, and subsequently, the steps of the production method of the present invention will be described.
[ resist composition ]
The resist composition (hereinafter also referred to as "specific resist composition") that can be produced by the production method of the present invention contains at least a photoacid generator containing a specific photoacid generator, an acid-decomposable resin (a)), and a solvent.
The specific resist composition may be either a positive type resist composition or a negative type resist composition. The resist composition may be an alkaline development resist composition or an organic solvent development resist composition.
The particular resist composition is typically a chemically amplified resist composition.
Hereinafter, first, the various components of a specific resist composition will be described in detail.
< photoacid generator >)
A specific resist composition contains a compound that generates an acid by irradiation of actinic rays or radiation (photoacid generator).
In the specific resist composition, the content of the photoacid generator (when plural kinds are contained, the total content thereof) is preferably 5.0 to 25.0% by mass, more preferably 8.0 to 20.0% by mass, relative to the total solid content of the composition. The content of the photoacid generator referred to herein refers to the total content (mass%) of the specific photoacid generator and the other photoacid generators, for example, in the case where the photoacid generator contained in the specific resist composition is both the specific photoacid generator described later and the other photoacid generator other than the specific photoacid generator described later.
In the present specification, the term "solid component" in the resist composition means a component forming a resist film, and does not include a solvent. Further, as long as the resist film is formed, the resist film is considered to be a solid even if the resist film is in a liquid state.
The photoacid generator includes a compound (specific photoacid generator) selected from the group consisting of compounds (I) to (III) described later.
The content of the specific photoacid generator (when plural types are contained, the total content thereof) is preferably 5.0 to 25.0% by mass, more preferably 8.0 to 20.0% by mass, relative to the total solid content of the composition.
The specific photoacid generator may be used alone or in combination of 1 or more than 2.
Hereinafter, a specific photoacid generator and other photoacid generators will be described.
(specific photoacid generator)
The specific photoacid generator is a compound selected from the group consisting of compounds (I) to (III) described later. The following describes compounds (I) to (III), respectively.
Compound (I)
The compound (I) will be described below.
Compound (I): is a compound which has 1 each of the following structural sites X and Y and generates an acid containing the following 1 st acid site derived from the following structural site X and the following 2 nd acid site derived from the following structural site Y by irradiation with actinic rays or radioactive rays,
Structural part X: from anionic site A 1 - Cation site M 1 + Composition, and by irradiation of actinic rays or radiation, form HA 1 The structural part of the 1 st acid part is shown,
structural part Y: from anionic site A 2 - Cation site M 2 + A composition of HA which is formed by irradiation with actinic rays or radiation and HAs a structure different from the 1 st acidic site formed at the structural site X 2 The structural part of the 2 nd acid part
Wherein the compound (I) satisfies the following condition I,
condition I: in the above compound (I), the above cation site M in the above structural site X 1 + And the cationic site M in the structural site Y 2 + Take the place of H + The resulting compound PI has: the acid dissociation constant a1 is derived from the cation site M in the structural site X 1 + Take the place of H + Made of HA 1 An acidic moiety represented; and an acid dissociation constant a2 derived from the cation site M in the structural site Y 2 + Take the place of H + Made of HA 2 The acid site represented by the formula (I),the acid dissociation constant a2 is larger than the acid dissociation constant a1.
The acid dissociation constant a1 and the acid dissociation constant a2 were obtained by the above-described method. The acid dissociation constants a1 and a2 of the compound PI will be described more specifically, and when the acid dissociation constant of the compound PI is determined, the compound PI (the compound PI corresponds to "having HA 1 HA (HA) 2 Is a compound of formula (I). ) Becomes "having A 1 - HA (HA) 2 The pKa of the compound "of (2) is the acid dissociation constant a1, and the above-mentioned" has A 1 - HA (HA) 2 The compounds "become" having A 1 - A is a 2 - The pKa at which the compound of (a) is present is the acid dissociation constant a2.
The compound PI corresponds to an acid generated by irradiation of the compound (I) with actinic rays or radiation.
In the compound PI, the difference between the acid dissociation constant a1 and the acid dissociation constant a2 is preferably 2.0 or more, more preferably 3.0 or more, from the viewpoint of more excellent LWR performance of the formed pattern. The upper limit of the difference between the acid dissociation constant a1 and the acid dissociation constant a2 is not particularly limited, and is, for example, 15.0 or less.
In addition, in the compound PI, the acid dissociation constant a2 is, for example, 6.5 or less, and is preferably 2.0 or less, more preferably 1.0 or less, from the viewpoint of further excellent stability of the compound (I) at the cationic site in the resist composition. The lower limit of the acid dissociation constant a2 is, for example, -3.5 or more, preferably, -2.0 or more.
Further, in the compound PI, the acid dissociation constant a1 is preferably 2.0 or less, more preferably 0.5 or less, and further preferably-0.1 or less, from the viewpoint of further excellent LWR performance of the formed pattern. The lower limit of the acid dissociation constant a1 is preferably-15.0 or more.
The compound (I) is not particularly limited, and examples thereof include compounds represented by the following general formula (Ia).
M 11 + A 11 - -L 1 -A 12 - M 12 + (Ia)
In the general formula (Ia), "M 11 + A 11 - "and" A 12 - M 12 + "corresponds to the structural part X and the structural part Y, respectively. The compound (Ia) is produced by irradiation of actinic rays or radiation 11 -L 1 -A 21 And H. Namely, "M 11 + A 11 - "formation of HA 11 The 1 st acid site "A" is represented by 12 - M 12 + "formed of HA having a structure different from that of the 1 st acid part 12 The 2 nd acidic site is shown.
In the general formula (Ia), M 11 + M and M 12 + Each independently represents an organic cation.
A 11 - A is a 12 - Each independently represents an anionic functional group. Wherein A is 12 - Representation and representation of A 11 - The anionic functional groups represented are different structures.
L 1 Represents a 2-valent linking group.
Wherein in the above general formula (Ia), the reaction is carried out by M 11 + M and M 12 + Represented organic cations are replaced by H + The resulting compound PIa (HA 11 -L 1 -A 12 H) Is derived from A 12 The acid dissociation constant a2 of the acid site represented by H is larger than that derived from HA 11 The acid dissociation constant a1 of the acid site is shown. In addition, preferable values of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above.
In the general formula (Ia), M is 11 + M and M 12 + The organic cations represented are as follows.
As a result of A 11 - A is a 12 - Examples of the anionic functional group include groups represented by the following general formulae (B-1) to (B-13).
[ chemical formula 2]
In the general formulae (B-1), (B-2), (B-4), (B-5) and (B-12), R X1 Represents a substituent.
As R X1 Preferably a linear, branched or cyclic alkyl group.
The number of carbon atoms of the alkyl group is preferably 1 to 15, more preferably 1 to 10.
The above alkyl group may have a substituent. The substituent is preferably a fluorine atom or a cyano group. When the above alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.
In the alkyl group, a carbon atom may be substituted with a carbonyl group.
In the general formula (B-3), R X4 Represents a substituent.
As R X4 Preferably a linear, branched or cyclic alkyl group.
The number of carbon atoms of the alkyl group is preferably 1 to 15, more preferably 1 to 10.
The above alkyl group may have a substituent. The substituent is preferably a fluorine atom or a cyano group. In addition, when R X4 When the alkyl group has a fluorine atom as a substituent, it is not preferably a perfluoroalkyl group.
In the alkyl group, a carbon atom may be substituted with a carbonyl group.
In the general formulae (B-7) and (B-11), R X2 Represents a hydrogen atom or a substituent other than a fluorine atom or a perfluoroalkyl group.
As represented by R X2 The substituent other than the fluorine atom and the perfluoroalkyl group is preferably a linear, branched or cyclic alkyl group.
The number of carbon atoms of the alkyl group is preferably 1 to 15, more preferably 1 to 10.
The above alkyl group may have a substituent other than a fluorine atom.
In the general formula (B-8), R XF1 Represents a hydrogen atom, a fluorine atom or a perfluoroalkyl group. Wherein a plurality of R XF1 At least one of which representsFluorine atoms or perfluoroalkyl groups.
From R XF1 The number of carbon atoms of the perfluoroalkyl group is preferably 1 to 15, more preferably 1 to 10, and still more preferably 1 to 6.
In the general formula (B-10), R XF2 Represents a fluorine atom or a perfluoroalkyl group.
From R XF2 The number of carbon atoms of the perfluoroalkyl group is preferably 1 to 15, more preferably 1 to 10, and still more preferably 1 to 6.
In the general formula (B-9), n represents an integer of 0 to 4.
As a result of A 11 - A is a 12 - The combination of the anionic functional groups represented is not particularly limited, for example, when A 11 - Is a group represented by the general formula (B-8) or (B-10) as represented by A 12 - Examples of the anionic functional group represented by the general formulae (B-1) to (B-7), general formula (B-9) or general formulae (B-11) to (B-13), when A 11 - Is a group represented by the general formula (B-7) as represented by A 12 - Examples of the anionic functional group include groups represented by the general formula (B-6).
In the general formula (Ia), L is 1 The represented 2-valent linking group is not particularly limited, examples include-CO-, -NR-, -CO-, -O-; alkylene groups (preferably having 1 to 6 carbon atoms, may be straight-chain, branched), cycloalkylene (preferably having 3 to 15 carbon atoms), alkenylene (preferably having 2 to 6 carbon atoms), aliphatic heterocyclic group having 2 valences (preferably a 5 to 10 membered ring having at least one N atom, O atom, S atom or Se atom in the ring structure, more preferably a 5 to 7 membered ring, still more preferably a 5 to 6 membered ring), and a 2-valent linking group obtained by combining a plurality of these groups. R may be a hydrogen atom or a substituent having a valence of 1. The substituent having a valence of 1 is not particularly limited, and is preferably an alkyl group (preferably having 1 to 6 carbon atoms).
These 2-valent linking groups may also comprise a moiety selected from the group consisting of-S-, -SO-and-SO 2 -a group of the group consisting of.
The alkylene group, the cycloalkylene group, the alkenylene group, and the 2-valent aliphatic heterocyclic group may be substituted with a substituent. Examples of the substituent include a halogen atom (preferably a fluorine atom).
In the general formula (Ia), the pair consists of M 11 + M and M 12 + The preferred form of the organic cation is described in detail.
From M 11 + M and M 12 + The organic cations represented by the general formula (ZaI) or the general formula (ZaII) (cation (ZaI)) are each independently preferable.
[ chemical formula 3]
R 204 -| + -R 205 (ZaII)
In the above-mentioned general formula (ZaI),
R 201 、R 202 r is R 203 Each independently represents an organic group.
As R 201 、R 202 R is R 203 The number of carbon atoms of the organic group of (2) is usually 1 to 30, preferably 1 to 20. And R is 201 ～R 203 The 2 groups may be bonded to form a ring structure, or may contain an oxygen atom, a sulfur atom, an ester group, an amide group or a carbonyl group in the ring. As R 201 ～R 203 Examples of the groups formed by bonding 2 of the above groups include alkylene groups (e.g., butylene and pentylene) and-CH 2 -CH 2 -O-CH 2 -CH 2 -。
Preferable examples of the organic cation in the general formula (ZaI) include a cation (ZaI-1), a cation (ZaI-2), an organic cation represented by the general formula (ZaI-3 b) (cation (ZaI-3 b)), and an organic cation represented by the general formula (ZaI-4 b) (cation (ZaI-4 b)) described later.
First, a cation (ZaI-1) will be described.
The cation (ZaI-1) is as described aboveR in the general formula (ZaI) 201 ～R 203 At least one of which is an aryl sulfonium cation of an aryl group.
In the aryl sulfonium cation, R can be 201 ～R 203 All being aryl groups, or R 201 ～R 203 Part of which is aryl, and the rest is alkyl or cycloalkyl.
And R is 201 ～R 203 Wherein 1 is aryl, R 201 ～R 203 The remaining 2 of the groups may be bonded to form a ring structure, or may contain an oxygen atom, a sulfur atom, an ester group, an amide group or a carbonyl group in the ring. As R 201 ～R 203 Examples of the group formed by bonding 2 of (a) include alkylene groups in which 1 or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group and/or a carbonyl group (e.g., butylene, pentylene or-CH) 2 -CH 2 -O-CH 2 -CH 2 -)。
Examples of the aryl sulfonium cation include triarylsulfonium cations, diarylalkyl sulfonium cations, aryl dialkyl sulfonium cations, diarylmethyl sulfonium cations, and aryl dicycloalkyl sulfonium cations.
The aryl group contained in the aryl sulfonium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure such as an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the aryl sulfonium cation has 2 or more aryl groups, the 2 or more aryl groups may be the same or different.
The alkyl group or cycloalkyl group of the aryl sulfonium cation is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, as required, and examples thereof include methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, and cyclohexyl.
As R 201 ～R 203 The aryl, alkyl and cycloalkyl groups in (a) may have substitutionExamples of the group include an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having 6 to 14 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a cycloalkylalkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group, independently of each other.
The substituent may have a substituent, for example, the alkyl group may have a halogen atom as a substituent, and may be a halogenated alkyl group such as a trifluoromethyl group.
Next, the cation (ZaI-2) will be described.
Cation (ZaI-2) is R in formula (ZaI) 201 ～R 203 Each independently represents a cation of an organic group having no aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a heteroatom.
As R 201 ～R 203 The organic group having no aromatic ring is usually 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R 201 ～R 203 Each independently is preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear or branched 2-oxo-alkyl group, a 2-oxo-cycloalkyl group or an alkoxycarbonylmethyl group, and still more preferably a linear or branched 2-oxo-alkyl group.
As R 201 ～R 203 Examples of the alkyl group and cycloalkyl group include a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl and pentyl) and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl and norbornyl).
R 201 ～R 203 May be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group or a nitro group.
Next, the cation (ZaI-3 b) will be described.
The cation (ZaI-3 b) is a cation represented by the following general formula (ZaI-3 b).
[ chemical formula 4]
In the general formula (ZaI-3 b),
R 1c ～R 5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group.
R 6c R is R 7c Each independently represents a hydrogen atom, an alkyl group (t-butyl group, etc.), a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R x R is R y Each independently represents alkyl, cycloalkyl, 2-oxoalkyl, 2-oxocycloalkyl, alkoxycarbonylalkyl, allyl or vinyl.
R 1c ～R 5c More than 2 of any one of R 5c And R is R 6c 、R 6c And R is R 7c 、R 5c And R is R x R is as follows x And R is R y May be bonded to form rings each independently containing an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Examples of the ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic condensed ring obtained by combining 2 or more of these rings. The ring may be a 3-to 10-membered ring, preferably a 4-to 8-membered ring, more preferably a 5-or 6-membered ring.
As R 1c ～R 5c More than 2 of any one of R 6c And R is R 7c R is as follows x And R is R y Examples of the group formed by bonding include alkylene groups such as butylene and pentylene. The methylene group in the alkylene group may be substituted with a hetero atom such as an oxygen atom.
As R 5c And R is R 6c R is as follows 5c And R is R x The group formed by bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.
Next, the cation (ZaI-4 b) will be described.
The cation (ZaI-4 b) is a cation represented by the following general formula (ZaI-4 b).
[ chemical formula 5]
In the general formula (ZaI-4 b),
l represents an integer of 0 to 2.
r represents an integer of 0 to 8.
R 13 Represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group (the cycloalkyl group itself may be a group partially containing a cycloalkyl group). These groups may have a substituent.
R 14 Represents a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group (which may be a cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have a substituent. When there are a plurality of R 14 In this case, each of the above groups independently represents a hydroxyl group or the like.
R 15 Each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent. 2R 15 Can be bonded to each other to form a ring. When 2R 15 When the two are bonded to each other to form a ring, a hetero atom such as an oxygen atom or a nitrogen atom may be contained in the ring skeleton. In one embodiment, 2R are preferred 15 Is alkylene, and is bonded to each other to form a ring structure.
In the general formula (ZaI-4 b), R 13 、R 14 R is R 15 The alkyl group of (2) is linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10. The alkyl group is more preferably a methyl group, an ethyl group, an n-butyl group, a tert-butyl group, or the like.
Next, the general formula (ZaII) will be described.
In the general formula (ZaII), R 204 R is R 205 Each independently represents aryl, alkyl or cycloalkyl.
As R 204 R is R 205 Preferably phenyl or naphthyl, more preferably phenyl. R is R 204 R is R 205 The aryl group of (a) may be an aryl group containing a heterocyclic ring having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
As R 204 R is R 205 The alkyl group and cycloalkyl group of (a) are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl or pentyl) or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl or norbornyl).
R 204 R is R 205 The aryl, alkyl and cycloalkyl groups of (a) may each independently have a substituent. As R 204 R is R 205 Examples of the substituent that may be contained in the aryl group, the alkyl group and the cycloalkyl group include an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group and a phenylthio group.
Compound (II)
Next, the compound (II) will be described.
Compound (II): is a compound having the structural site Y and 2 or more of the structural sites X and generating an acid containing the 2 nd acid site derived from the structural site Y and 2 or more of the 1 st acid site derived from the structural site X by irradiation with actinic rays or radiation
Wherein the compound (II) satisfies the following condition II,
condition II: in the above-mentioned compound (II), the above-mentioned cation site M in the above-mentioned structural site X 1 + A cation site M in the structural site Y 2 + Take the place of H + The resulting compound PII has: the acid dissociation constant a1 is derived from the cation site M in the structural site X 1 + Take the place of H + Made of HA 1 An acidic moiety represented; and an acid dissociation constant a2 derived from the cation site M in the structural site Y 2 + Take the place of H + Made of HA 2 The acid site represented, and the acid dissociation constant a2 is larger than the acid dissociation constant a1.
The acid dissociation constant a1 and the acid dissociation constant a2 were obtained by the above-described method.
Here, the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PII will be described more specifically. When the compound (II) is, for example, a compound producing an acid having 2 acid sites 1 derived from the structural site X and 1 acid site 2 derived from the structural site Y, the compound PII corresponds to "having 2 HA 1 And HA (alpha) 2 Is a compound of formula (I). When the acid dissociation constant of the compound PII was determined, the compound PII became "having 1A 1 - 1 HA 1 And HA (alpha) 2 The pKa of the compound "of (2) is the acid dissociation constant a1," having 2A 1 - And HA (alpha) 2 The compounds "become" having 2A 1 - And A 2 - The pKa at which the compound of (a) is present is the acid dissociation constant a2. That is, when the compound PII has a plurality of cationic sites M derived from the structural site X 1 + Take the place of H + Made of HA 1 The minimum value of the acid dissociation constant of the acid site is regarded as the acid dissociation constant a1.
The compound PII corresponds to an acid generated by irradiation of the compound (II) with actinic rays or radiation.
The compound (II) may have a plurality of the above-mentioned structural sites Y.
In the above-described compound PII, the difference between the acid dissociation constant a1 and the acid dissociation constant a2 is preferably 2.0 or more, more preferably 3.0 or more, from the viewpoint of more excellent LWR performance of the formed pattern. The upper limit of the difference between the acid dissociation constant a1 and the acid dissociation constant a2 is not particularly limited, and is, for example, 15.0 or less.
In the above-mentioned compound PII, the acid dissociation constant a2 is, for example, 6.5 or less, and is preferably 2.0 or less, more preferably 1.0 or less, from the viewpoint of further excellent stability of the compound (I) at the cationic site in the resist composition. The lower limit of the acid dissociation constant a2 is, for example, -3.5 or more, preferably, -2.0 or more.
In the above-mentioned compound PII, the acid dissociation constant a1 is preferably 2.0 or less, more preferably 0.5 or less, and even more preferably-0.1 or less, from the viewpoint of further excellent LWR performance of the formed pattern. The lower limit of the acid dissociation constant a1 is preferably-15.0 or more.
The compound (II) is not particularly limited, and examples thereof include compounds represented by the following general formula (IIa).
[ chemical formula 6]
In the general formula (Ia), "M 21 + A 21 - "and" A 22 - M 22 + "corresponds to the structural part X and the structural part Y, respectively. The compound (IIa) generates an acid represented by the following general formula (IIa-1) upon irradiation with actinic rays or radiation. Namely, "M 21 + A 21 - "formation of HA 21 The 1 st acid site "A" is represented by 22 - M 22 + "formed of HA having a structure different from that of the 1 st acid part 22 The 2 nd acidic site is shown.
[ chemical formula 7]
In the general formula (IIa), M 21 + M and M 22 + Each independently represents an organic cation.
A 21 - A is a 22 - Each independently represents an anionic functional group. Wherein A is 22 - Representation and representation of A 21 - The anionic functional groups represented are different structures.
L 2 An organic group having a valence of (n1+n2).
n1 represents an integer of 2 or more.
n2 represents an integer of 1 or more.
Wherein in the above formula (IIa), the reaction is carried out by M 21 + M and M 22 + Represented organic cations are replaced by H + The compound PIIa (corresponding to the compound represented by the general formula (IIa-1)) is derived from A 22 The acid dissociation constant a2 of the acid site represented by H is larger than that derived from HA 21 The acid dissociation constant a1 of the acid site is shown. In addition, preferable values of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above.
In the above formula (IIa), M 21 + 、M 22 + 、A 21 - A is a 22 - Respectively M in the general formula (Ia) 11 + 、M 12 + 、A 11 - A is a 12 - The meaning of (2) is the same, and the preferred mode is the same.
In the above formula (IIa), n 1M 21 + Each other, n 1A 21 + Each of which represents the same group as each other.
In the above formula (IIa), L is 2 The organic group having a valence of (n1+n2) is not particularly limited, and examples thereof include groups represented by the following (A1) and (A2). In the following (A1) and (A2), at least 2 of them represent the same group as a 21 - At least one of which represents a bond with a 22 - Is used for the bonding position of the substrate.
[ chemical formula 8]
The above (A1)(A2) In T 1 Represents a hydrocarbon ring group having a valence of 3 or a heterocyclic group having a valence of 3, T 2 Represents a carbon atom, a 4-valent hydrocarbon ring group or a 4-valent heterocyclic group.
The hydrocarbon ring group may be an aromatic hydrocarbon ring group or an aliphatic hydrocarbon ring group. The number of carbon atoms contained in the hydrocarbon ring group is preferably 6 to 18, more preferably 6 to 14.
The heterocyclic group may be an aromatic heterocyclic group or an aliphatic heterocyclic group. The heterocyclic ring is preferably a 5-to 10-membered ring having at least one of an N atom, an O atom, an S atom, and a Se atom in the ring structure, more preferably a 5-to 7-membered ring, and still more preferably a 5-to 6-membered ring.
In the above (A1) and (A2), L 21 L and L 22 Each independently represents a single bond or a 2-valent linking group.
As represented by L 21 L and L 22 A 2-valent linking group represented by the general formula (Ia) above and a group represented by L 1 The meaning of the 2-valent linking groups indicated is the same, preferably in the same manner.
n1 represents an integer of 2 or more. The upper limit is not particularly limited, and is, for example, 6 or less, preferably 4 or less, and more preferably 3 or less.
n2 represents an integer of 1 or more. The upper limit is not particularly limited, but is, for example, 3 or less, preferably 2 or less.
Compound (III)
Next, the compound (III) will be described.
Compound (III): is a compound having a structural part Z and 2 or more structural parts X and generating an acid containing the structural part Z and 2 or more 1 st acid parts derived from the structural part X by irradiation with actinic rays or radiation
Structural part Z: a nonionic moiety capable of neutralizing an acid.
The nonionic moiety capable of neutralizing the acid in the structural moiety Z is not particularly limited, and examples thereof include organic moieties, and for example, organic moieties having a functional group capable of electrostatically interacting with protons or electrons are preferable.
Examples of the functional group having a group or an electron capable of electrostatic interaction with a proton include a functional group having a macrocyclic compound structure such as a cyclic polyether, or a functional group having a nitrogen atom with an unshared electron pair that does not contribute to pi conjugation. The nitrogen atom having an unshared pair of electrons that does not contribute to pi conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.
[ chemical formula 9]
Examples of the partial structure having a functional group capable of electrostatically interacting with a proton or an electron include a crown ether structure, an aza crown ether structure, a primary amine structure, a secondary amine structure, a tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure, and among these, a primary amine structure, a secondary amine structure, and a tertiary amine structure are preferable.
In the above compound (III), the cation site M in the structural site X 1 + Take the place of H + The resulting compound PIII is derived from the cationic site M in the structural site X from the viewpoint of more excellent LWR performance of the formed pattern 1 + Take the place of H + Made of HA 1 The acid dissociation constant a1 of the acid site is preferably 2.0 or less, more preferably 0.5 or less, and further preferably-0.1 or less. The lower limit of the acid dissociation constant a1 is preferably-15.0 or more.
In addition, when the compound PIII has a plurality of cationic sites M derived from the structural site X 1 + Take the place of H + Made of HA 1 The minimum value of the acid dissociation constant of the acid site is regarded as the acid dissociation constant a1.
That is, when the compound (III) is, for example, a compound generating an acid having 2 acid sites derived from the 1 st acid site of the structural site X and the structural site ZThe PIII equivalent "HAs 2 HA' s 1 Is a compound of formula (I). When the acid dissociation constant of the compound PIII was determined, the compound PIII became "having 1A 1 - And 1 HA 1 The pKa at which the compound of (a) is present is the acid dissociation constant a1. That is, when the compound PIII has a plurality of cationic sites M derived from the structural site X 1 + Take the place of H + Made of HA 1 The minimum value of the acid dissociation constant of the acid site is regarded as the acid dissociation constant a1.
In the compound (III), the cation site M in the structural site X is replaced with 1 + Take the place of H + The compound PIII is, for example, a compound represented by the following compound (IIIa) when the compound (III) is a compound corresponding to HA 31 -L 3 -N(R 2X )-L 4 -A 31 H。
The compound (III) is not particularly limited, and examples thereof include compounds represented by the following general formula (IIIa).
[ chemical formula 10]
In the general formula (IIIa), "M 31 + A 31 - "corresponds to the structural site X". The compound (IIIa) is produced by irradiation of actinic rays or radiation 31 -L 3 -N(R 2X )-L 4 -A 31 And H. Namely, "M 31 + A 31 - "formation of HA 31 The 1 st acid site is shown.
In the general formula (IIIa), M 31 + Representing an organic cation.
A 31 - Represents an anionic functional group.
L 3 L and L 4 Each independently represents a 2-valent linking group.
R 2X Represents a substituent having a valence of 1.
In the above formula (IIIa), M 31 + A is a 31 - Respectively M in the general formula (Ia) 11 + A is a 11 - The meaning of (2) is the same, and the preferred mode is the same.
In the above formula (IIIa), L 3 L and L 4 Respectively with L in the general formula (Ia) 1 The meaning of (2) is the same, and the preferred mode is the same.
In the above formula (IIIa), 2M 31 + Each other and 2A 31 - Each of which represents the same group as each other.
In the general formula (IIIa), R is 2X The substituent having 1 valence is not particularly limited, and examples thereof include-CH 2 Can be selected from the group consisting of-CO-, -NH-, -O-, -S-, -SO-and-SO 2 1 or 2 or more kinds of the groups are substituted in combination, and alkyl (preferably having 1 to 10 carbon atoms, linear or branched), cycloalkyl (preferably having 3 to 15 carbon atoms), alkenyl (preferably having 2 to 6 carbon atoms), and the like.
The alkylene group, the cycloalkylene group, and the alkenylene group may be substituted with a substituent.
The molecular weight of the compounds represented by the above-mentioned compounds (I) to (III) is preferably 300 or more and less than 3000, more preferably 500 to 2000, and still more preferably 700 to 1500.
Preferred examples of the compounds represented by the above-mentioned compounds (I) to (III) are shown below.
[ chemical formula 11]
/>
[ chemical formula 12]
[ chemical formula 13]
(other photoacid generators)
The photoacid generator other than the specific photoacid generator, which may be contained as the specific resist composition, is not particularly limited. Examples of the other photoacid generator include known compounds disclosed in paragraphs [0125] to [0319] of U.S. patent application publication 2016/007167A 1, paragraphs [0086] to [0094] of U.S. patent application publication 2015/0004544A1, paragraphs [0323] to [0402] of U.S. patent application publication 2016/0237190A1, and paragraphs [0074] to [0122] and [0137] to [0146] of Japanese patent application laid-open No. 2018-155788.
When the specific resist composition contains other photoacid generator, the content of the other photoacid generator is preferably 0.1 to 10.0 mass% with respect to the total solid content of the composition.
The other photoacid generator may be used alone or in combination of 1 or 2 or more. When 2 or more kinds are used, the total content thereof is preferably within the above-mentioned preferred content range.
< acid-decomposable resin (A)) >
The specific resist composition contains a resin (hereinafter, also referred to as "acid-decomposable resin" or "resin (a)") which is decomposed by the action of an acid to increase the polarity.
That is, in the pattern forming method of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed.
The resin (a) generally contains a group (hereinafter, also referred to as "acid-decomposable group") whose polarity increases by decomposition by the action of an acid, and preferably contains a repeating unit having an acid-decomposable group.
Repeating units having acid-decomposable groups
The acid-decomposable group refers to a group that is decomposed by the action of an acid to produce a polar group. The acid-decomposable group preferably has a structure in which a polar group is protected by a release group released by the action of an acid. That is, the resin (a) contains a repeating unit having a group that generates a polar group by decomposition by the action of an acid. The resin having the repeating unit increases in polarity by the action of an acid, so that the solubility in an alkaline developer increases, and the solubility in an organic solvent decreases.
The polar group is preferably an alkali-soluble group, and examples thereof include acidic groups such as carboxyl group, phenolic hydroxyl group, fluorinated alcohol group, sulfonic acid group, phosphoric acid group, sulfonamide group, sulfonylimino group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group and tris (alkylsulfonyl) methylene group, and alcoholic hydroxyl group.
Among them, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably hexafluoroisopropanol group), or a sulfonic acid group.
Examples of the releasing group released by the action of an acid include groups represented by formulae (Y1) to (Y4).
Formula (Y1): -C (Rx) 1 )(Rx 2 )(Rx 3 )
Formula (Y2): -C (=o) OC (Rx 1 )(Rx 2 )(Rx 3 )
Formula (Y3): -C (R) 36 )(R 37 )(OR 38 )
Formula (Y4): c (Rn) (H) (Ar) A-5,
in the formula (Y1) and the formula (Y2), rx 1 ～Rx 3 Each independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). In addition, when Rx 1 ～Rx 3 When all of (a) are alkyl groups (straight chain or branched), rx is preferable 1 ～Rx 3 At least 2 of which are methyl groups.
Of these, rx is preferred 1 ～Rx 3 Each independently represents a linear or branched alkyl group, more preferably Rx 1 ～Rx 3 Each independently represents a linear alkyl group.
Rx 1 ～Rx 3 Or 2 of them may be bonded to form a single ring or multiple rings.
As Rx 1 ～Rx 3 The alkyl group of (a) is preferably an alkyl group having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl groups.
As Rx 1 ～Rx 3 Preferred cycloalkyl groups include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl.
As Rx 1 ～Rx 3 The aryl group of (2) is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl and anthracenyl.
As Rx 1 ～Rx 3 Alkenyl groups of (2) are preferably vinyl groups.
As Rx 1 ～Rx 3 The ring formed by bonding 2 of these are preferably cycloalkyl groups. As Rx 1 ～Rx 3 The cycloalkyl group bonded to 2 of the above groups is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl or adamantyl, more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.
Rx 1 ～Rx 3 Of cycloalkyl groups formed by bonding, for example, 1 of methylene groups constituting the ring may be substituted with a group having a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or a vinylidene group. Of these cycloalkyl groups, 1 or more of the ethylene groups constituting the cycloalkyl ring may be substituted with a vinyl group (vinyl).
The group represented by the formula (Y1) or the formula (Y2) is preferably, for example, rx 1 Is methyl or ethyl, and Rx 2 With Rx 3 Bonding to form the cycloalkyl group.
In the formula (Y3), R 36 ～R 38 Each independently represents a hydrogen atom or a 1-valent organic group. R is R 37 And R is R 38 Can be bonded to each other to form a ring. Examples of the 1-valent organic group include an alkyl group,Cycloalkyl, aryl, aralkyl, alkenyl, and the like. R is R 36 Hydrogen atoms are also preferred.
The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and/or a heteroatom such as a carbonyl group. For example, in the above alkyl group, cycloalkyl group, aryl group and aralkyl group, for example, 1 or more of methylene groups may be substituted with a heteroatom such as an oxygen atom and/or a heteroatom such as a carbonyl group.
And R is 38 Can bond with another substituent group of the main chain of the repeating unit to form a ring. R is R 38 The group formed by bonding with another substituent on the main chain of the repeating unit is preferably an alkylene group such as a methylene group.
The formula (Y3) is preferably a group represented by the following formula (Y3-1).
[ chemical formula 14]
Here, L 1 L and L 2 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining them (for example, a group formed by combining an alkyl group and an aryl group).
M represents a single bond or a 2-valent linking group.
Q represents an alkyl group which may contain a heteroatom, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group which is a combination thereof (for example, a group which is a combination of an alkyl group and a cycloalkyl group).
In the alkyl group and the cycloalkyl group, for example, 1 of the methylene groups may be substituted with a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.
In addition, L is preferable 1 L and L 2 One of which is a hydrogen atom and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining an alkylene group with an aryl group.
Q, M and L 1 At least 2 of which may be bondedForming a ring (preferably a 5-membered ring or a 6-membered ring).
L is preferable from the viewpoint of miniaturization of the pattern 2 Is a secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of the secondary alkyl group include isopropyl, cyclohexyl and norbornyl groups, and examples of the tertiary alkyl group include tertiary butyl and adamantyl groups. In these modes, tg (glass transition temperature) and activation energy increase, so that film strength can be ensured and blurring can be suppressed.
In the formula (Y4), ar represents an aromatic ring group. Rn represents alkyl, cycloalkyl or aryl. Rn and Ar may bond to each other to form a non-aromatic ring. Ar is more preferably aryl.
From the viewpoint of excellent acid degradability of the repeating unit, it is also preferable that, when the non-aromatic ring is directly bonded to the polar group (or a residue thereof) in the protecting group for the polar group, a ring member adjacent to a ring member directly bonded to the polar group (or a residue thereof) in the non-aromatic ring does not have a halogen atom such as a fluorine atom as a substituent.
Further, the release group released by the action of an acid may also be a 2-cyclopentenyl group having a substituent (alkyl group or the like) such as a 3-methyl-2-cyclopentenyl group, and a cyclohexyl group having a substituent (alkyl group or the like) such as a 1, 4-tetramethylcyclohexyl group.
The repeating unit having an acid-decomposable group is also preferably a repeating unit represented by the formula (a).
[ chemical formula 15]
L 1 Represents a 2-valent linking group which may have a fluorine atom or an iodine atom, R 1 Represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom, R 2 Represents a group which is detached by the action of an acid and may have a fluorine atom or an iodine atom. Wherein L is 1 、R 1 R is R 2 At least one of them hasThere are fluorine atoms or iodine atoms.
L 1 Represents a 2-valent linking group which may have a fluorine atom or an iodine atom. As the 2-valent linking group which may have a fluorine atom or an iodine atom, can be exemplified by-CO-, -O-; -S-, -SO 2 And a linking group formed by linking a plurality of hydrocarbon groups (e.g., alkylene, cycloalkylene, alkenylene, arylene, etc.) which may have a fluorine atom or an iodine atom. Wherein, as L 1 preferably-CO-or-arylene-alkylene having a fluorine atom or an iodine atom.
As the arylene group, a phenylene group is preferable.
The alkylene group may be linear or branched. The number of carbon atoms of the alkylene group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3.
The total number of fluorine atoms and iodine atoms contained in the alkylene group having fluorine atoms or iodine atoms is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and still more preferably 3 to 6.
R 1 Represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom.
The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3.
The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and still more preferably 1 to 3.
The alkyl group may contain a hetero atom such as an oxygen atom other than a halogen atom.
R 2 Represents a group which is detached by the action of an acid and may have a fluorine atom or an iodine atom.
Among them, examples of the releasing group include groups represented by the formulas (Z1) to (Z4).
Formula (Z1): -C (Rx) 11 )(Rx 12 )(Rx 13 ) Formula (Z2): -C (=o) OC (Rx 11 )(Rx 12 )(Rx 13 ) Formula (Z3): -C (R) 136 )(R 137 )(OR 138 ) Formula (Z4): -C (Rn) 1 )(H)(Ar 1 )
In the formulas (Z1) and (Z2), rx 11 ～Rx 13 Each independently represents an alkyl group (linear or branched) which may have a fluorine atom or an iodine atom, a cycloalkyl group (monocyclic or polycyclic) which may have a fluorine atom or an iodine atom, an alkenyl group (linear or branched) which may have a fluorine atom or an iodine atom, or an aryl group (monocyclic or polycyclic) which may have a fluorine atom or an iodine atom. In addition, when Rx 11 ～Rx 13 When all of the alkyl groups are straight or branched, rx is preferable 11 ～Rx 13 At least 2 of which are methyl groups.
Rx 11 ～Rx 13 Except that the fluorine atom or iodine atom may be contained, rx in the above formulae (Y1) and (Y2) 1 ～Rx 3 The same as the definition and preferred ranges for alkyl, cycloalkyl, alkenyl and aryl groups.
In the formula (Z3), R 136 ～R 138 Each independently represents a hydrogen atom or a 1-valent organic group that may have a fluorine atom or an iodine atom. R is R 137 And R is R 138 Can be bonded to each other to form a ring. Examples of the 1-valent organic group which may have a fluorine atom or an iodine atom include an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, an aralkyl group which may have a fluorine atom or an iodine atom, and a group combining them (for example, a group combining an alkyl group with a cycloalkyl group).
In addition to fluorine atoms and iodine atoms, hetero atoms such as oxygen atoms may be contained in the alkyl group, cycloalkyl group, aryl group, and aralkyl group. That is, in the above alkyl group, cycloalkyl group, aryl group and aralkyl group, for example, 1 of the methylene groups may be substituted with a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.
And R is 138 Can bond with another substituent group of the main chain of the repeating unit to form a ring. At this time, R 138 Backbone with repeating unitsThe group formed by bonding the other substituent is preferably an alkylene group such as a methylene group.
As the formula (Z3), a group represented by the following formula (Z3-1) is preferable.
[ chemical formula 16]
Here, L 11 L and L 12 Each independently represents a hydrogen atom; an alkyl group which may have a heteroatom selected from the group consisting of fluorine atom, iodine atom and oxygen atom; cycloalkyl groups which may have a heteroatom selected from the group consisting of fluorine atom, iodine atom and oxygen atom; an aryl group which may have a heteroatom selected from the group consisting of fluorine atom, iodine atom and oxygen atom; or a group formed by combining them (for example, a group formed by combining an alkyl group and a cycloalkyl group, which may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom).
M 1 Represents a single bond or a 2-valent linking group.
Q 1 An alkyl group which may have a heteroatom selected from the group consisting of fluorine atom, iodine atom and oxygen atom; cycloalkyl groups which may have a heteroatom selected from the group consisting of fluorine atom, iodine atom and oxygen atom; an aryl group which may have a heteroatom selected from the group consisting of fluorine atom, iodine atom and oxygen atom; an amino group; an ammonium group; a mercapto group; cyano group; an aldehyde group; or a group formed by combining them (for example, a group formed by combining an alkyl group and a cycloalkyl group, which may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom).
Ar in formula (Z4) 1 Represents an aromatic ring group which may have a fluorine atom or an iodine atom. Rn 1 Represents an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. Rn 1 With Ar 1 Can be bonded to each other to form a non-aromatic ring.
The repeating unit having an acid-decomposable group is also preferably a repeating unit represented by the general formula (AI).
[ chemical formula 17]
In the general formula (AI) as described above,
Xa 1 represents a hydrogen atom or an alkyl group which may have a substituent.
T represents a single bond or a 2-valent linking group.
Rx 1 ～Rx 3 Each independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). Wherein when Rx 1 ～Rx 3 When all of the alkyl groups are straight or branched, rx is preferable 1 ～Rx 3 At least 2 of which are methyl groups.
Rx 1 ～Rx 3 May be bonded to form a single ring or multiple rings (a single ring or multiple ring cycloalkyl group).
As a result of Xa 1 The alkyl group which may have a substituent(s) represented by the formula (I) may be, for example, methyl or-CH 2 -R 11 A group represented by the formula (I). R is R 11 Examples of the organic group which represents a halogen atom (fluorine atom or the like), a hydroxyl group or a 1-valent organic group include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkyl group having 3 or less carbon atoms is preferable, and a methyl group is more preferable. As Xa 1 Preferably a hydrogen atom, methyl, trifluoromethyl or hydroxymethyl group.
Examples of the 2-valent linking group for T include an alkylene group, an aromatic ring group, -COO-Rt-group, and-O-Rt-group. Wherein Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or-COO-Rt-group. When T represents a-COO-Rt-group, rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably-CH 2 -group, - (CH) 2 ) 2 -group or- (CH) 2 ) 3 -a radical.
As Rx 1 ～Rx 3 The alkyl group of (a) is preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl.
As Rx 1 ～Rx 3 Preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl or adamantyl.
As Rx 1 ～Rx 3 The aryl group of (2) is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl and anthracenyl.
As Rx 1 ～Rx 3 Alkenyl groups of (2) are preferably vinyl groups.
As Rx 1 ～Rx 3 Cycloalkyl groups bonded to 2 of the above groups are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl are also preferred. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferable.
Rx 1 ～Rx 3 Of cycloalkyl groups formed by bonding, for example, 1 of methylene groups constituting the ring may be substituted with a group having a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or a vinylidene group. Of these cycloalkyl groups, 1 or more of the ethylene groups constituting the cycloalkyl ring may be substituted with a vinyl group (vinyl).
The repeating unit represented by the general formula (AI) is preferably, for example, rx 1 Is methyl or ethyl, and Rx 2 With Rx 3 Bonding to form the cycloalkyl group.
When each of the above groups has a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms), and the like. The number of carbon atoms in the substituent is preferably 8 or less.
As the repeating unit represented by the general formula (AI), an acid moiety is preferableA hydrolyzable tertiary alkyl (meth) acrylate repeating unit (Xa) 1 Represents a hydrogen atom or a methyl group, and T represents a repeating unit of a single bond).
The content of the repeating unit having an acid-decomposable group is preferably 15 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more, with respect to all the repeating units in the resin (a). The upper limit is preferably 80 mol% or less, more preferably 70 mol% or less, and particularly preferably 60 mol% or less.
Specific examples of the repeating unit having an acid-decomposable group are shown below, but the present invention is not limited thereto. In addition, in the formula Xa 1 Representation H, CH 3 、CF 3 CH (CH) 2 OH and Rxa and Rxb each represent a linear or branched alkyl group having 1 to 5 carbon atoms.
[ chemical formula 18]
[ chemical formula 19]
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[ chemical formula 20]
[ chemical formula 21]
[ chemical formula 22]
The resin (a) may contain a repeating unit other than the repeating unit.
For example, the resin (a) may also contain at least one repeating unit selected from the group consisting of the following group a and/or at least one repeating unit selected from the group consisting of the following group B.
Group A: the group consisting of the following repeating units (20) to (29).
(20) Repeating units having an acid group as described later
(21) Repeating units having fluorine or iodine atoms, to be described later
(22) Repeating units having lactone, sultone or carbonate groups as described later
(23) Repeating units having photoacid generating groups as described later
(24) The repeating unit represented by the following general formula (V-1) or the following general formula (V-2)
(25) The repeating unit represented by the formula (A)
(26) The repeating unit represented by the formula (B)
(27) The repeating unit represented by the formula (C)
(28) The repeating unit represented by the formula (D)
(29) A repeating unit group B represented by formula (E): a group consisting of the following repeating units (30) to (32).
(30) The repeating unit having at least one group selected from the group consisting of a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group and an alkali-soluble group
(31) Repeating units having alicyclic hydrocarbon structure and exhibiting no acid decomposition property, which will be described later
(32) The repeating unit represented by the general formula (III) having no one of a hydroxyl group and a cyano group
When a specific resist composition is used as the resist composition for EUV, the resin (a) preferably has at least one repeating unit selected from the group consisting of the above-mentioned group a.
When a specific resist composition is used as the EUV resist composition, the resin (a) preferably contains at least one of fluorine atoms and iodine atoms. When the resin (a) contains both fluorine atoms and iodine atoms, the resin (a) may have 1 repeating unit containing both fluorine atoms and iodine atoms, and the resin (a) may contain 2 repeating units containing fluorine atoms and repeating units containing iodine atoms.
When a specific resist composition is used as the EUV resist composition, the resin (a) preferably further contains a repeating unit having an aromatic group.
When a specific resist composition is used as the resist composition for ArF, the resin (a) preferably has at least one repeating unit selected from the group consisting of the above-mentioned group B.
In addition, when a specific resist composition is used as the resist composition for ArF, the resin (a) preferably does not contain any one of fluorine atoms and silicon atoms.
Further, when a specific resist composition is used as the resist composition for ArF, the resin (a) preferably has no aromatic group.
Repeating units having acid groups
The resin (a) may contain a repeating unit having an acid group.
The acid group is preferably an acid group having a pKa of 13 or less.
Examples of the acid group include a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, and an isopropanol group.
In the hexafluoroisopropanol group, 1 or more (preferably 1 to 2) of the fluorine atoms may be substituted with a group other than a fluorine atom (e.g., an alkoxycarbonyl group). Thus formed-C (CF) 3 )(OH)-CF 2 Also preferred as acid groups. In addition, 1 or more of the fluorine atoms may be substituted with groups other than fluorine atoms to form a group containing-C (CF) 3 )(OH)-CF 2 -a ring.
The repeating unit having an acid group is preferably a repeating unit different from the repeating unit including: a repeating unit having a structure in which a polar group is protected by a release group released by the action of the acid; and a repeating unit having a lactone group, a sultone group or a carbonate group, which will be described later.
The repeating unit having an acid group may have a fluorine atom or an iodine atom.
The repeating unit having an acid group is preferably a repeating unit represented by the formula (B).
[ chemical formula 23]
R 3 An organic group having a valence of 1, which represents a hydrogen atom or may have a fluorine atom or an iodine atom.
As the 1-valent organic group which may have a fluorine atom or an iodine atom, a group consisting of-L is preferable 4 -R 8 A group represented by the formula (I). L (L) 4 Represents a single bond or an ester group. R is R 8 Examples thereof include an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a combination thereof.
R 4 R is R 5 Each independently represents a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group which may have a fluorine atom or an iodine atom.
L 2 Represents a single bond or an ester group.
L 3 An aromatic hydrocarbon ring group having a valence of (n+m+1) or an alicyclic hydrocarbon ring group having a valence of (n+m+1). Examples of the aromatic hydrocarbon ring group include a benzene ring group and a naphthalene ring group. The alicyclic hydrocarbon ring group may be a single ring or a plurality of rings, and examples thereof include cycloalkyl ring groups.
R 6 Represents a hydroxyl group or a fluorinated alcohol group (preferably hexafluoroisopropanol group). In addition, when R 6 When hydroxyl is L 3 An aromatic hydrocarbon ring group having a valence of (n+m+1) is preferable.
R 7 Represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
m represents an integer of 1 or more. m is preferably an integer of 1 to 3, more preferably an integer of 1 to 2.
n represents an integer of 0 or 1 or more. n is preferably an integer of 1 to 4.
Further, (n+m+1) is preferably an integer of 1 to 5.
The repeating unit having an acid group is also preferably a repeating unit represented by the following general formula (I).
[ chemical formula 24]
In the general formula (I),
R 41 、R 42 r is R 43 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Wherein R is 42 Can be combined with Ar 4 Bonding to form a ring, R at this time 42 Represents a single bond or an alkylene group.
X 4 Represents a single bond, -COO-or-CONR 64 -，R 64 Represents a hydrogen atom or an alkyl group.
L 4 Represents a single bond or an alkylene group.
Ar 4 Represents an aromatic ring group having a valence of (n+1), when it is bonded to R 42 When bonded to form a ring, the aromatic ring group having a valence of (n+2) is represented.
n represents an integer of 1 to 5.
R as in the general formula (I) 41 、R 42 R is R 43 The alkyl group of (a) is preferably an alkyl group having 20 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, or a dodecyl group, more preferably an alkyl group having 8 or less carbon atoms, and still more preferably an alkyl group having 3 or less carbon atoms.
R as in the general formula (I) 41 、R 42 R is R 43 The cycloalkyl group of (2) may be a monocyclic or polycyclic one. Among them, cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl and cyclohexyl and having a single ring type are preferable.
R as in the general formula (I) 41 、R 42 R is R 43 The halogen atom of (2) may be a fluorine atom or a chlorine atomThe proton, bromine atom and iodine atom are preferably fluorine atoms.
R as in the general formula (I) 41 、R 42 R is R 43 The alkyl group contained in the alkoxycarbonyl group of (2) is preferably the same as R 41 、R 42 R is R 43 The same alkyl group as the alkyl group in (a).
Preferred substituents among the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, urea groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, cyano groups, and nitro groups. The number of carbon atoms of the substituent is preferably 8 or less.
Ar 4 Represents an aromatic ring group having a valence of (n+1). The 2-valent aromatic ring group in the case where n is 1 is preferably a 2-valent aromatic ring group containing a heterocycle, such as a phenylene group, a tolylene group, a naphthylene group, an anthracenylene group, or the like, or a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, or a thiazole ring. The aromatic ring group may have a substituent.
Specific examples of the (n+1) -valent aromatic ring group in the case where n is an integer of 2 or more include those obtained by removing (n-1) arbitrary hydrogen atoms from the above-mentioned specific examples of the 2-valent aromatic ring group.
The (n+1) -valent aromatic ring group may have a substituent.
Examples of the substituents which may be present in the alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group and (n+1) valent aromatic ring group include R in the general formula (I) 41 、R 42 R is R 43 Alkoxy groups such as alkyl groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, and butoxy groups; aryl groups such as phenyl; etc.
As represented by X 4 represented-CONR 64 -(R 64 Represents a hydrogen atom or an alkyl group) 64 Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl and 2-ethylhexylAlkyl groups having 20 or less carbon atoms such as a group, an octyl group and a dodecyl group are preferable, and alkyl groups having 8 or less carbon atoms are preferable.
As X 4 Preferably a single bond, -COO-or-CONH-, more preferably a single bond or-COO-.
As L 4 The alkylene group in (a) is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group.
As Ar 4 The aromatic ring group having 6 to 18 carbon atoms is preferable, and the benzene ring group, naphthalene ring group and biphenylene (biphenene) ring group are more preferable.
The repeating unit represented by the general formula (I) preferably has a hydroxystyrene structure. Namely Ar 4 Benzene ring groups are preferred.
The repeating unit represented by the general formula (I) is preferably a repeating unit represented by the following general formula (1).
[ chemical formula 25]
In the general formula (1),
a represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group.
R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, and when a plurality of R's are present, they may be the same or different. With a plurality of R, they may form a ring together with each other. R is preferably a hydrogen atom.
a represents an integer of 1 to 3.
b represents an integer of 0 to (5-a).
The repeating unit having an acid group is exemplified below. Wherein a represents 1 or 2.
[ chemical formula 26]
[ chemical formula 27]
[ chemical formula 28]
Among the repeating units, the repeating units described below are preferable. Wherein R represents a hydrogen atom or a methyl group, and a represents 2 or 3.
[ chemical formula 29]
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[ chemical formula 30]
The content of the repeating unit having an acid group is preferably 10 mol% or more, more preferably 15 mol% or more, with respect to all the repeating units in the resin (a). The upper limit is preferably 70 mol% or less, more preferably 65 mol% or less, and still more preferably 60 mol% or less.
Repeating units having fluorine or iodine atoms
Unlike the above-mentioned "repeating unit having an acid-decomposable group" and "repeating unit having an acid group", the resin (a) may contain a repeating unit having a fluorine atom or an iodine atom. The "repeating unit having a fluorine atom or an iodine atom" herein is preferably different from other types of repeating units belonging to group a, such as "repeating units having a lactone group, a sultone group or a carbonate group" and "repeating units having a photoacid generator group" described later.
The repeating unit having a fluorine atom or an iodine atom is preferably a repeating unit represented by the formula (C).
[ chemical formula 31]
L 5 Represents a single bond or an ester group.
R 9 Represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom.
R 10 Represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a combination thereof.
The repeating unit having a fluorine atom or an iodine atom is exemplified below.
[ chemical formula 32]
The content of the repeating unit having a fluorine atom or an iodine atom is preferably 0 mol% or more, more preferably 5 mol% or more, and still more preferably 10 mol% or more, with respect to all the repeating units in the resin (a). The upper limit is preferably 50 mol% or less, more preferably 45 mol% or less, and still more preferably 40 mol% or less.
In addition, as described above, since the repeating unit having a fluorine atom or an iodine atom does not include the "repeating unit having an acid-decomposable group" and the "repeating unit having an acid group", the content of the repeating unit having a fluorine atom or an iodine atom "described above also means the content of the repeating unit having a fluorine atom or an iodine atom other than the" repeating unit having an acid-decomposable group "and the" repeating unit having an acid group ".
The total content of repeating units containing at least one of fluorine atoms and iodine atoms in the repeating units of the resin (a) is preferably 20 mol% or more, more preferably 30 mol% or more, and still more preferably 40 mol% or more, with respect to all the repeating units of the resin (a). The upper limit is not particularly limited, and is, for example, 100 mol% or less.
Examples of the repeating unit containing at least one of a fluorine atom and an iodine atom include a repeating unit having a fluorine atom or an iodine atom and having an acid-decomposable group, a repeating unit having a fluorine atom or an iodine atom and having an acid group, and a repeating unit having a fluorine atom or an iodine atom.
Repeating units having lactone, sultone or carbonate groups
The resin (a) may contain a repeating unit having at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group (hereinafter, also collectively referred to as "a repeating unit having a lactone group, a sultone group, or a carbonate group").
The repeating unit having a lactone group, a sultone group or a carbonate group preferably does not have an acid group such as a hexafluoropropanol group.
The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5-7 membered ring lactone structure or a 5-7 membered ring sultone structure. Of these, a structure in which another ring structure is condensed on a 5-to 7-membered ring lactone structure in the form of a double ring structure or a spiro ring structure, or a structure in which another ring structure is condensed on a 5-to 7-membered ring sultone structure in the form of a double ring structure or a spiro ring structure is more preferable.
The resin (A) preferably contains a repeating unit having a lactone group or a sultone group, wherein 1 or more hydrogen atoms are extracted from ring members of a lactone structure represented by any one of the following general formulae (LC 1-1) to (LC 1-21) or a sultone structure represented by any one of the following general formulae (SL 1-1) to (SL 1-3).
Also, the lactone group or sultone group may be directly bonded to the main chain. For example, the ring member of the lactone group or the sultone group may constitute the main chain of the resin (a).
[ chemical formula 33]
The lactone structure or sultone structure moiety may have a substituent (Rb) 2 ). As a preferred substituent (Rb) 2 ) Examples thereof include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, an acid-decomposable group, and the like. n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of Rb are present 2 May be different and there are a plurality of Rb 2 May bond to each other to form a ring.
Examples of the repeating unit including a group having a lactone structure represented by any one of the general formulae (LC 1-1) to (LC 1-21) or a sultone structure represented by any one of the general formulae (SL 1-1) to (SL 1-3) include a repeating unit represented by the following general formula (AI).
[ chemical formula 34]
In the general formula (AI), rb 0 Represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms.
As Rb 0 Preferred substituents which may be included in the alkyl group of (a) include hydroxyl groups and halogen atoms.
As Rb 0 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Rb (Rb) 0 Preferably a hydrogen atom or a methyl group.
Ab represents a single bond, an alkylene group, a 2-valent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a 2-valent group formed by combining them. Of these, preferred is a single bond or a bond consisting of-Ab 1 -CO 2 -a linking group represented. Ab (Ab) 1 Is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene groupA base or a sub-norbornyl group.
V represents a group in which 1 hydrogen atom is extracted from the ring member of the lactone structure represented by any one of the general formulae (LC 1-1) to (LC 1-21), or a group in which 1 hydrogen atom is extracted from the ring member of the sultone structure represented by any one of the general formulae (SL 1-1) to (SL 1-3).
When an optical isomer exists in a repeating unit having a lactone group or a sultone group, any optical isomer may be used. Further, 1 kind of optical isomer may be used alone, or a plurality of kinds of optical isomers may be used in combination. When 1 optical isomer is mainly used, the optical purity (ee) thereof is preferably 90 or more, more preferably 95 or more.
The carbonate group is preferably a cyclic carbonate group.
The repeating unit having a cyclic carbonate group is preferably a repeating unit represented by the following general formula (A-1).
[ chemical formula 35]
In the general formula (A-1), R A 1 Represents a hydrogen atom, a halogen atom or a 1-valent organic group (preferably a methyl group).
n represents an integer of 0 or more.
R A 2 Represents a substituent. When n is 2 or more, there are a plurality of R A 2 May be the same or different.
A represents a single bond or a 2-valent linking group. The above-mentioned 2-valent linking group is preferably an alkylene group, a 2-valent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a 2-valent group formed by combining them.
Z represents an atomic group forming a single ring or multiple rings together with the group represented by-O-CO-O-in the formula.
The repeating unit having a lactone group, a sultone group or a carbonate group is exemplified below.
[ chemical formula 36]
[ chemical formula 37]
[ chemical formula 38]
The content of the repeating unit having a lactone group, a sultone group or a carbonate group is preferably 1 mol% or more, more preferably 10 mol% or more, with respect to all the repeating units in the resin (a). The upper limit is preferably 85 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, and particularly preferably 60 mol% or less.
Repeating units having photoacid generator groups
The resin (a) may contain a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as a "photoacid generator group") as a repeating unit other than the above.
In this case, the repeating unit having the photoacid generator group is considered to correspond to a compound that generates an acid upon irradiation with actinic rays or radiation (also referred to as a "photoacid generator").
Examples of such a repeating unit include a repeating unit represented by the following general formula (4).
[ chemical formula 39]
R 41 Represents a hydrogen atom or a methyl group. L (L) 41 Representing a single bond orA 2-valent linking group. L (L) 42 Represents a 2-valent linking group. R is R 40 The structural site is decomposed by irradiation with actinic rays or radiation to generate an acid in the side chain.
The following examples illustrate repeating units having photoacid generator groups.
[ chemical formula 40]
[ chemical formula 41]
Examples of the repeating unit represented by the general formula (4) include repeating units described in paragraphs [0094] to [0105] of JP-A2014-04327.
The content of the repeating unit having a photoacid generator group is preferably 1 mol% or more, more preferably 5 mol% or more, with respect to all the repeating units in the resin (a). The upper limit is preferably 40 mol% or less, more preferably 35 mol% or less, and still more preferably 30 mol% or less.
Repeating units represented by the general formula (V-1) or the following general formula (V-2)
The resin (A) may have a repeating unit represented by the following general formula (V-1) or the following general formula (V-2).
The repeating unit represented by the following general formula (V-1) and the following general formula (V-2) is preferably a repeating unit different from the repeating unit described above.
[ chemical formula 42]
In the method, in the process of the invention,
R 6 r is R 7 Each independently represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, or a nitro groupA group, an amino group, a halogen atom, an ester group (-OCOR or-COOR: R is an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group) or a carboxyl group. The alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
n 3 An integer of 0 to 6.
n 4 And represents an integer of 0 to 4.
X 4 Is methylene, oxygen atom or sulfur atom.
The repeating unit represented by the general formula (V-1) or (V-2) is exemplified below.
[ chemical formula 43]
Repeating units for reducing the motility of the Main chain
From the viewpoint of being able to suppress excessive diffusion of the generated acid or pattern disintegration upon development, the resin (a) preferably has a high glass transition temperature (Tg). The Tg is preferably greater than 90℃and more preferably greater than 100℃and even more preferably greater than 110℃and particularly preferably greater than 125 ℃. Further, too high Tg leads to a decrease in dissolution rate in the developer, and therefore Tg is preferably 400℃or less, more preferably 350℃or less.
In the present specification, the glass transition temperature (Tg) of a polymer such as the resin (a) is calculated by the following method. First, tg of a homopolymer consisting only of each repeating unit contained in the polymer was calculated by the Bicerano method, respectively. The calculated Tg is hereinafter referred to as "repeating unit Tg". Next, the mass ratio (%) of each repeating unit to all repeating units in the polymer was calculated. Next, tg in each mass ratio is calculated using Fox formula (Materials Letters, 62 (2008) 3152, etc.), and the sum of these is set as Tg (°c) of the polymer.
Bicerano method is described in predictions of polymer properties (Prediction of polymer properties), marcel Dekker Inc, new York (1993), etc. The Tg calculation by the Bicerano method can be performed using Polymer physical property estimation software MDL Polymer (MDL Information Systems, inc.).
In order to increase the Tg of the resin (A) (preferably to make the Tg more than 90 ℃), it is preferable to decrease the mobility of the main chain of the resin (A). The method of reducing the mobility of the main chain of the resin (A) includes the following methods (a) to (e).
(a) Introduction of bulky substituents into the main chain
(b) Introducing multiple substituents into the main chain
(c) Introduction of substituents initiating interactions between resins (A) near the main chain
(d) Forming a backbone in a cyclic structure
(e) Linking cyclic structures to the main chain
In addition, the resin (A) preferably has a repeating unit having a Tg of a homopolymer of 130 ℃ or higher.
The type of the repeating unit having a Tg of 130 ℃ or higher in the homopolymer is not particularly limited, as long as the Tg of the homopolymer calculated by the Bicerano method is 130 ℃ or higher. The type of functional group in the repeating unit represented by the following formulas (a) to (E) corresponds to a repeating unit having a Tg of 130 ℃ or higher in the homopolymer.
(repeating units represented by the formula (A))
As an example of a specific implementation means of the above (a), a method of introducing a repeating unit represented by the formula (a) into the resin (a) is given.
[ chemical formula 44]
In the formula (A), R A Represents a group having a polycyclic structure. R is R x Represents a hydrogen atom, a methyl group or an ethyl group. The group having a polycyclic structure is a group having a plurality of ring structures, which may or may not be condensed.
Specific examples of the repeating unit represented by the formula (a) include the following repeating units.
[ chemical formula 45]
[ chemical formula 46]
[ chemical formula 47]
In the above formula, R represents a hydrogen atom, a methyl group or an ethyl group.
Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR ' "or-COOR '": R ' "is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group) or a carboxyl group. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. The hydrogen atom bonded to the carbon atom in the group represented by Ra may be replaced with a fluorine atom or an iodine atom.
R ' and R ' each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR ' "or-COOR '": R ' "is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group), or a carboxyl group. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. The hydrogen atom bonded to the carbon atom in the group represented by R' and r″ may be replaced with a fluorine atom or an iodine atom.
L represents a single bond or a 2-valent linking group. As the 2-valent linking group, for example, examples include-COO-, -CO-; -O-, -S-, -SO 2 -, a part of alkylene group cycloalkylene radical alkenylene group, a linking group formed by linking a plurality of alkenylene groups, and the like。
m and n each independently represent an integer of 0 or more. The upper limits of m and n are not particularly limited, but are usually 2 or less, and 1 or less in many cases.
(repeating units represented by the formula (B))
As an example of a specific implementation means of the above (B), a method of introducing a repeating unit represented by the formula (B) into the resin (a) is given.
[ chemical formula 48]
In the formula (B), R b1 ～R b4 Each independently represents a hydrogen atom or an organic group, R b1 ～R b4 At least 2 or more of them represent an organic group.
Also, when at least one of the organic groups is a group in which a ring structure is directly connected to the main chain of the repeating unit, the kind of other organic groups is not particularly limited.
In the case where none of the organic groups is a group in which a ring structure is directly linked to the main chain in the repeating unit, at least 2 or more of the organic groups are substituents having 3 or more constituent atoms other than hydrogen atoms.
Specific examples of the repeating unit represented by the formula (B) include the following repeating units.
[ chemical formula 49]
/>
In the above formula, R each independently represents a hydrogen atom or an organic group. Examples of the organic group include organic groups such as alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups, which may have a substituent.
R 'independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR' or-COOR ': R' is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group) or a carboxyl group. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. Further, the hydrogen atom bonded to the carbon atom in the group represented by R' may be substituted with a fluorine atom or an iodine atom.
m represents an integer of 0 or more. The upper limit of m is not particularly limited, but is usually 2 or less, and 1 or less is more often used.
(repeating units represented by the formula (C))
As an example of a specific implementation means of the above (C), a method of introducing a repeating unit represented by the formula (C) into the resin (a) is given.
[ chemical formula 50]
In the formula (C), R c1 ～R c4 Each independently represents a hydrogen atom or an organic group, R c1 ～R c4 At least one of (2) is a group having a hydrogen-bonding hydrogen atom within 3 atoms from the main chain carbon. Among them, it is preferable that the resin (a) has hydrogen-bonding hydrogen atoms in an atomic number of 2 or less (closer to the main chain side) in addition to causing interaction between the main chains.
Specific examples of the repeating unit represented by the formula (C) include the following repeating units.
[ chemical formula 51]
In the above formula, R represents an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, and an ester group (-OCOR or-COOR: R is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group) which may have a substituent.
R' represents a hydrogen atom or an organic group. Examples of the organic group include an organic group such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. In addition, the hydrogen atom in the organic group may be substituted with a fluorine atom or an iodine atom.
(repeating units represented by the formula (D))
As an example of a specific implementation means of the above (D), a method of introducing a repeating unit represented by the formula (D) into the resin (a) is given.
[ chemical formula 52]
/>
In the formula (D), "Cyclic" means a group having a Cyclic structure to form a main chain. The number of ring constituent atoms is not particularly limited.
Specific examples of the repeating unit represented by the formula (D) include the following repeating units.
[ chemical formula 53]
In the above formula, R independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR ' or-COOR ': R ' is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group), or a carboxyl group. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. The hydrogen atom bonded to the carbon atom in the group represented by R may be replaced with a fluorine atom or an iodine atom.
In the above formula, R 'independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR' or-COOR ': R' is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group), or a carboxyl group. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. Further, the hydrogen atom bonded to the carbon atom in the group represented by R' may be substituted with a fluorine atom or an iodine atom.
m represents an integer of 0 or more. The upper limit of m is not particularly limited, but is usually 2 or less, and 1 or less is more often used.
(repeating units represented by the formula (E))
As an example of a specific implementation means of the above (E), a method of introducing a repeating unit represented by the formula (E) into the resin (a) is given.
[ chemical formula 54]
In the formula (E), re each independently represents a hydrogen atom or an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, and the like which may have a substituent.
"Cyclic" is a Cyclic group containing carbon atoms in the backbone. The number of atoms contained in the cyclic group is not particularly limited.
Specific examples of the repeating unit represented by the formula (E) include the following repeating units.
[ chemical formula 55]
[ chemical formula 56]
In the above formula, R independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR ' or-COOR ': R ' is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group), or a carboxyl group. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. The hydrogen atom bonded to the carbon atom in the group represented by R may be replaced with a fluorine atom or an iodine atom.
R 'independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR' or-COOR ': R' is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group), or a carboxyl group. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. Further, the hydrogen atom bonded to the carbon atom in the group represented by R' may be substituted with a fluorine atom or an iodine atom.
m represents an integer of 0 or more. The upper limit of m is not particularly limited, but is usually 2 or less, and 1 or less is more often used.
In the formulae (E-2), (E-4), (E-6) and (E-8), 2R groups may be bonded to each other to form a ring.
The content of the repeating unit represented by the formula (E) is preferably 5 mol% or more, more preferably 10 mol% or more, with respect to all the repeating units in the resin (a). The upper limit is preferably 60 mol% or less, and more preferably 55 mol% or less.
Repeating units having at least one group selected from the group consisting of a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group and an alkali-soluble group
The resin (a) may contain a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group.
Examples of the repeating unit having a lactone group, a sultone group or a carbonate group included in the resin (a) include the repeating unit described in the above "repeating unit having a lactone group, a sultone group or a carbonate group". The preferable content is also as described in the above-mentioned "repeating unit having a lactone group, a sultone group or a carbonate group".
The resin (a) may contain a repeating unit having a hydroxyl group or a cyano group. This improves the substrate adhesion and the developer affinity.
The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group.
The repeating unit having a hydroxyl group or a cyano group preferably has no acid-decomposable group. Examples of the repeating unit having a hydroxyl group or a cyano group include repeating units represented by the following general formulae (AIIa) to (AIId).
[ chemical formula 57]
In the general formulae (AIIa) to (AIId),
R 1c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
R 2c ～R 4c Each independently represents a hydrogen atom, a hydroxyl group or a cyano group. Wherein R is 2c ～R 4c Represents a hydroxyl group or a cyano group. Preferably R 2c ～R 4c 1 or 2 of them are hydroxyl groups, and the balance thereof are hydrogen atoms. More preferably R 2c ～R 4c 2 of which are hydroxyl groups and the balance of which are hydrogen atoms.
The content of the repeating unit having a hydroxyl group or a cyano group is preferably 5 mol% or more, more preferably 10 mol% or more, with respect to all the repeating units in the resin (a). The upper limit is preferably 40 mol% or less, more preferably 35 mol% or less, and still more preferably 30 mol% or less.
Specific examples of the repeating unit having a hydroxyl group or a cyano group are given below, but the present invention is not limited thereto.
[ chemical formula 58]
The resin (a) may also contain a repeating unit having an alkali-soluble group.
Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol group (for example, hexafluoroisopropanol group) in which the α -position is substituted with an electron withdrawing group, and preferably a carboxyl group. By making the resin (a) contain a repeating unit having an alkali-soluble group, resolution in contact hole use is improved.
Examples of the repeating unit having an alkali-soluble group include a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit formed of acrylic acid and methacrylic acid, and a repeating unit in which an alkali-soluble group is bonded to the main chain of the resin through a linking group. In addition, the linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure.
As the repeating unit having an alkali-soluble group, a repeating unit formed of acrylic acid or methacrylic acid is preferable.
The content of the repeating unit having an alkali-soluble group is preferably 0 mol% or more, more preferably 3 mol% or more, and still more preferably 5 mol% or more, with respect to all the repeating units in the resin (a). The upper limit is preferably 20 mol% or less, more preferably 15 mol% or less, and still more preferably 10 mol% or less.
Specific examples of the repeating unit having an alkali-soluble group are shown below, but the present invention is not limited thereto. In one embodiment, rx represents H, CH 3 、CH 2 OH or CF 3 。
[ chemical formula 59]
The repeating unit having at least one group selected from the group consisting of a lactone group, a hydroxyl group, a cyano group and an alkali-soluble group is preferably a repeating unit having at least 2 groups selected from the group consisting of a lactone group, a hydroxyl group, a cyano group and an alkali-soluble group, more preferably a repeating unit having a cyano group and a lactone group, and still more preferably a repeating unit having a structure substituted with a cyano group in the lactone structure represented by the general formula (LC 1-4).
Repeating units having an alicyclic hydrocarbon structure and exhibiting no acid decomposition
The resin (a) may contain a repeating unit having an alicyclic hydrocarbon structure and exhibiting no acid decomposition property. This reduces the elution of low molecular components from the resist film into the immersion liquid during immersion exposure. Examples of such a repeating unit include a repeating unit derived from 1-adamantyl (meth) acrylate, diamantanyl (meth) acrylate, tricyclodecane (meth) acrylate, and cyclohexyl (meth) acrylate.
A repeating unit having no hydroxyl group or cyano group and represented by the general formula (III)
The resin (a) may contain a repeating unit represented by the general formula (III) without any of a hydroxyl group and a cyano group.
[ chemical formula 60]
In the general formula (III), R 5 Represents a hydrocarbon group having at least one cyclic structure and not having any one of a hydroxyl group and a cyano group.
Ra represents a hydrogen atom, an alkyl group or-CH 2 -O-Ra 2 A base. Wherein Ra is 2 Represents a hydrogen atom, an alkyl group or an acyl group.
R 5 The cyclic structure of the catalyst contains a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include cycloalkyl groups having 3 to 12 carbon atoms (more preferably 3 to 7 carbon atoms) and cycloalkenyl groups having 3 to 12 carbon atoms.
Examples of the polycyclic hydrocarbon group include cyclic hydrocarbon groups and crosslinked cyclic hydrocarbon groups.
Examples of the crosslinked cyclic hydrocarbon ring include a 2-ring hydrocarbon ring, a 3-ring hydrocarbon ring, and a 4-ring hydrocarbon ring. The crosslinked hydrocarbon ring may also include a condensed ring in which a plurality of 5-to 8-membered cycloalkane rings are condensed.
The crosslinked cyclic hydrocarbon group is preferably norbornyl, adamantyl, bicyclooctyl or tricyclo [5, 2, 1, 0] 2,6 ]Decyl, more preferably norbornyl or adamantyl.
The alicyclic hydrocarbon group may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, and an amino group protected with a protecting group.
The halogen atom is preferably a bromine atom, a chlorine atom or a fluorine atom.
As the alkyl group, methyl, ethyl, butyl or tert-butyl is preferred. The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, and an amino group protected with a protecting group.
Examples of the protecting group include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkoxycarbonyl group.
As the alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable.
As the substituted methyl group, methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl or 2-methoxyethoxymethyl is preferred.
As the substituted ethyl group, 1-ethoxyethyl group or 1-methyl-1-methoxyethyl group is preferable.
The acyl group is preferably an aliphatic acyl group having 1 to 6 carbon atoms such as a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pentanoyl group or a pivaloyl group.
The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 4 carbon atoms.
The content of the repeating unit represented by the general formula (III) which does not have any one of a hydroxyl group and a cyano group is preferably 0 to 40 mol%, more preferably 0 to 20 mol%, with respect to all the repeating units in the resin (a).
Specific examples of the repeating unit represented by the general formula (III) are given below, but the present invention is not limited thereto. In a specific example, ra represents H, CH 3 、CH 2 OH or CF 3 。
[ chemical formula 61]
Other repeating units
The resin (a) may contain a repeating unit other than the repeating unit.
For example, the resin (a) may contain a repeating unit selected from the group consisting of a repeating unit having a thioxane (Oxathiane) ring group, a repeating unit having a hydroxy-mocoumarin (Oxazorone) ring group, a repeating unit having a dioxane ring group, and a repeating unit having a Hydantoin (Hydantoin) ring group.
Such a repeating unit is exemplified below.
[ chemical formula 62]
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In addition to the above-described repeating structural units, the resin (a) may have various repeating structural units for the purpose of adjusting dry etching resistance, standard developer adaptability, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like.
As the resin (A), (particularly when a specific resist composition is used as the resist composition for ArF), it is also preferable that all the repeating units are constituted of (meth) acrylate-based repeating units. In this case, any of the repeating units may be used, that is, all the repeating units are repeating units of a methacrylate-based repeating unit, all the repeating units are repeating units of an acrylate-based repeating unit, all the repeating units are repeating units formed of a methacrylate-based repeating unit and an acrylate-based repeating unit, and the acrylate-based repeating unit is preferably 50 mol% or less of all the repeating units.
The resin (a) can be synthesized according to a conventional method (e.g., radical polymerization).
The weight average molecular weight of the resin (a) is preferably 3,000 to 20,000, more preferably 5,000 to 15,000, as a polystyrene equivalent based on GPC. By setting the weight average molecular weight of the resin (a) to 3,000 ～ 200,000, deterioration of heat resistance and dry etching resistance can be further suppressed. Further, deterioration of film forming property due to deterioration of developing property and increase of viscosity can be suppressed.
The dispersity (molecular weight distribution) of the resin (a) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and further preferably 1.2 to 2.0. The smaller the dispersity, the more excellent the resolution and resist shape, and the smoother the sidewall of the resist pattern, the more excellent the roughness.
In the specific resist composition, the content of the resin (a) is preferably 50 to 99.9 mass%, more preferably 60 to 99.0 mass%, relative to the total solid content of the composition.
The solid component refers to a component other than the solvent in the composition, and is regarded as a solid component even if it is a liquid component as long as it is a component other than the solvent.
The resin (A) may be used in 1 kind, or a plurality of resins may be used in combination.
< acid diffusion controlling agent >)
The specific resist composition may further contain an acid diffusion controlling agent.
The acid diffusion controlling agent captures an acid generated from a photoacid generator or the like at the time of exposure and functions as a quencher that suppresses a reaction of the acid-decomposable resin in the unexposed portion due to the excessively generated acid. As the acid diffusion controlling agent, for example, an alkaline compound (DA), an alkaline compound (DB) in which the alkalinity is reduced or eliminated by irradiation with actinic rays or radiation, a low molecular compound (DD) having a nitrogen atom and having a group which is detached by the action of an acid, an onium salt compound (DE) having a nitrogen atom in the cation portion, and the like can be used. In the specific resist composition, a known acid diffusion control agent can be suitably used. For example, known compounds disclosed in paragraphs [0627] to [0664] in the specification of U.S. patent application publication 2016/007467A 1, paragraphs [0095] to [0187] in the specification of U.S. patent application publication 2015/0004544A1, paragraphs [0403] to [0423] in the specification of U.S. patent application publication 2016/0237190A1, and paragraphs [0259] to [0328] in the specification of U.S. patent application publication 2016/0274458A1 can be preferably used as the acid diffusion controlling agent.
(basic Compound (DA))
The basic compound (DA) is preferably a compound having a structure represented by the following formulas (a) to (E).
[ chemical formula 63]
In the general formula (A) and the general formula (E),
R 200 、R 201 r is R 202 And each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (preferably having 6 to 20 carbon atoms). R is R 201 And R is R 202 Can be bonded to each other to form a ring.
R 203 、R 204 、R 205 R is R 206 And each independently represents an alkyl group having 1 to 20 carbon atoms.
The alkyl group in the general formula (a) and the general formula (E) may have a substituent or may be unsubstituted.
As the alkyl group, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferable as the alkyl group having a substituent.
The alkyl groups in the general formulae (a) and (E) are more preferably unsubstituted.
The basic compound (DA) is preferably guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine or piperidine, more preferably an imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, a compound having an aniline structure or pyridine structure, an alkylamine derivative having a hydroxyl group and/or an ether bond, or an aniline derivative having a hydroxyl group and/or an ether bond.
(alkaline Compound (DB) in which alkalinity is reduced or eliminated by irradiation of actinic rays or radiation)
An alkali compound (DB) (hereinafter also referred to as "compound (DB)") having a proton acceptor functional group and having reduced or eliminated proton acceptors or changed to acidic form by decomposition by irradiation of actinic rays or radiation.
The proton acceptor functional group is a functional group having a group or an electron capable of electrostatically interacting with a proton, for example, a functional group representing a macrocyclic compound structure such as a cyclic polyether, or a functional group having a nitrogen atom with an unshared electron pair that does not contribute to pi conjugation. The nitrogen atom having an unshared pair of electrons that does not contribute to pi conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.
[ chemical formula 64]
Examples of preferred partial structures of the proton acceptor functional group include crown ether structures, aza crown ether structures, primary amine structures, secondary amine structures, tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures.
The compound (DB) generates a compound which is decomposed by irradiation with actinic rays or radiation to reduce or eliminate proton acceptors or to change from proton acceptors to acidity. Here, the decrease or disappearance of proton acceptors or the change from proton acceptors to acidity is a change in proton acceptors due to addition of protons to proton acceptors functional groups, and specifically, indicates that when proton adducts are generated from a compound (DB) having proton acceptors functional groups and protons, the equilibrium constant in the chemical equilibrium decreases.
Proton acceptors can be confirmed by performing pH measurements.
The acid dissociation constant (pKa) of the compound produced by decomposition of the compound (DB) by irradiation with actinic rays or radiation preferably satisfies pKa < 1, more preferably satisfies-13 < pKa < 1, and even more preferably satisfies-13 < pKa < 3.
The acid dissociation constant (pKa) can be obtained by the above method.
(Low molecular Compound (DD) having a nitrogen atom and having a group which is detached by the action of an acid)
The low molecular compound (DD) having a nitrogen atom and having a group that is detached by the action of an acid (hereinafter, also referred to as "compound (DD)") is preferably an amine derivative having a group that is detached by the action of an acid on a nitrogen atom.
The group to be released by the action of an acid is preferably an acetal group, a carbonate group, a urethane group, a tertiary ester group, a tertiary hydroxyl group or a semiacetal ether group, more preferably a urethane group or a semiacetal ether group.
The molecular weight of the compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and still more preferably 100 to 500.
The compound (DD) may have a urethane group having a protecting group on a nitrogen atom. The protecting group constituting the urethane group is represented by the following general formula (d-1).
[ chemical formula 65]
In the general formula (d-1),
R b each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group (preferably having 1 to 10 carbon atoms), or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms). R is R b Can be interconnected to form a ring.
R b The alkyl group, cycloalkyl group, aryl group, and aralkyl group may be each independently substituted with a functional group such as a hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, oxo group, or the like, an alkoxy group, or a halogen atom. For R b The same applies to the alkoxyalkyl groups represented.
As R b The alkyl group is preferably a linear or branched alkyl group, cycloalkyl group or aryl group, and more preferably a linear or branched alkyl group or cycloalkyl group.
As 2R b Examples of the ring formed by the connection include alicyclic hydrocarbon, aromatic hydrocarbon, heterocyclic hydrocarbon and derivatives thereof.
Specific examples of the structure of the group represented by the general formula (d-1) include, but are not limited to, the structure disclosed in paragraph [0466] in the specification of U.S. patent publication No. US2012/0135348A 1.
The compound (DD) is preferably a compound represented by the following general formula (6).
[ chemical formula 66]
In the general formula (6), the amino acid sequence,
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and l+m=3 is satisfied.
R a Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, 2R a May be the same or different, 2R a Or may be linked to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may contain a heteroatom other than the nitrogen atom in the formula.
R b Has the meaning as defined for R in the above formula (d-1) b The same applies to the preferred examples.
In the general formula (6), R is as follows a The alkyl, cycloalkyl, aryl and aralkyl groups of (a) may each independently be substituted with the same group as that described above as the group which may be used as R b Alkyl, cycloalkyl, aryl, and aralkyl substitution.
As R as above a Specific examples of the alkyl, cycloalkyl, aryl and aralkyl groups (these groups may be substituted with the above groups) include those mentioned above for R b The same groups as those in the above specific examples.
Specific examples of the particularly preferred compound (DD) in the present invention include, but are not limited to, the compounds disclosed in paragraph [0475] in specification of U.S. patent application publication 2012/0135348 A1.
(onium salt Compound (DE) having a Nitrogen atom in the cation portion)
The onium salt compound (DE) having a nitrogen atom in the cation portion (hereinafter, also referred to as "compound (DE)") is preferably a compound having a basic site containing a nitrogen atom in the cation portion. The basic moiety is preferably an amino group, more preferably an aliphatic amino group. It is further preferable that all of the atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. In addition, from the viewpoint of improving basicity, it is preferable that the functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) having electron withdrawing property is not directly connected to the nitrogen atom.
Preferred specific examples of the compound (DE) include, but are not limited to, the compounds disclosed in paragraph [0203] in the specification of U.S. patent application publication 2015/0309408A 1.
Preferred examples of the acid diffusion controlling agent are shown below.
[ chemical formula 67]
When the acid diffusion controlling agent is contained in the specific resist composition, the content of the acid diffusion controlling agent (when plural kinds are present, the total thereof) is preferably 0.1 to 11.0% by mass, more preferably 0.1 to 10.0% by mass, still more preferably 0.1 to 8.0% by mass, and particularly preferably 0.1 to 5.0% by mass, relative to the total solid content of the composition.
In the specific resist composition, 1 kind of the acid diffusion controlling agent may be used alone, or 2 or more kinds may be used in combination.
< hydrophobic resin >)
The specific resist composition may contain a hydrophobic resin other than the above resin (a) other than the resin (a).
The hydrophobic resin is preferably designed to be biased to the surface of the resist film, but unlike the surfactant, it is not necessarily required to have a hydrophilic group in the molecule, and it may not contribute to uniform mixing of the polar substance and the nonpolar substance.
Examples of the effect of adding the hydrophobic resin include control of static and dynamic contact angles of the resist film surface with respect to water, and suppression of outgas (outgas).
From the viewpoint of biasing the film surface layer, the hydrophobic resin preferably has "fluorine atom", "silicon atom", and "CH contained in the side chain portion of the resin 3 Any one of the partial structures "is 1 or more, and more preferably 2 or more. The hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted with a side chain.
When the hydrophobic resin contains fluorine atoms and/or silicon atoms, the fluorine atoms and/or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin or in the side chains.
When the hydrophobic resin contains a fluorine atom, an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom is preferable as a partial structure having a fluorine atom.
The alkyl group having a fluorine atom (preferably, a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably, 1 to 4 carbon atoms) may have a substituent other than a fluorine atom, and at least one hydrogen atom is substituted with a fluorine atom.
Cycloalkyl having a fluorine atom is a monocyclic or polycyclic cycloalkyl in which at least one hydrogen atom is substituted with a fluorine atom, and may have a substituent other than a fluorine atom.
Examples of the aryl group having a fluorine atom include groups in which at least one hydrogen atom of the aryl group such as a phenyl group and a naphthyl group is substituted with a fluorine atom, and may have a substituent other than a fluorine atom.
Examples of the repeating unit having a fluorine atom or a silicon atom include the repeating unit exemplified in paragraph [0519] in US2012/0251948 A1.
And, as described aboveIt is also preferable that the hydrophobic resin contains CH in the side chain portion 3 Partial structure.
Here, CH contained in the side chain portion of the hydrophobic resin 3 Part of the structure comprises CH of ethyl, propyl and the like 3 Partial structure.
On the other hand, a methyl group directly bonded to the main chain of the hydrophobic resin (for example, an α -methyl group having a repeating unit of a methacrylic acid structure) contributes little to surface localization of the hydrophobic resin due to the influence of the main chain, and therefore is regarded as a CH not included in the present invention 3 Partial structure.
The hydrophobic resin is described in paragraphs [0348] to [0415] of Japanese patent application laid-open No. 2014-010245, which are incorporated herein by reference.
In addition to these, the hydrophobic resins described in Japanese patent application laid-open No. 2011-248019, japanese patent application laid-open No. 2010-175859, and Japanese patent application laid-open No. 2012-032544 may be preferably used.
Preferred examples of the monomer corresponding to the repeating unit constituting the hydrophobic resin are shown below.
[ chemical formula 68]
[ chemical formula 69]
When the specific resist composition contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0% by mass, more preferably 0.1 to 15.0% by mass, further preferably 0.1 to 10.0% by mass, and particularly preferably 0.1 to 6.0% by mass, relative to the total solid content of the composition.
< surfactant >)
The particular resist composition may also contain a surfactant. By containing the surfactant, a pattern having more excellent adhesion and fewer development defects can be formed.
The surfactant is preferably a fluorine-based and/or silicon-based surfactant.
Examples of the fluorine-based and/or silicon-based surfactant include surfactants described in paragraph [0276] of U.S. patent application publication No. 2008/024825. Also, eftop EF301 or EF303 (manufactured by Shin-Akita Kasei co., ltd.) may be used; fluorad FC430, 431 or 4430 (manufactured by Sumitomo 3M Limited); megaface F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC CORPORATION); surflon S-382, SC101, 102, 103, 104, 105, or 106 (manufactured by ASAHI GLASS co., ltd.); troySol S-366 (manufactured by Troy Chemical Industries Inc.); GF-300 or GF-150 (manufactured by Toagosei Chemical co., ltd.), surflon S-393 (manufactured by SEIMI CHEMICAL co., ltd.); eftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, or EF601 (manufactured by Gemco co., ltd.); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA Solutions inc.); KH-20 (manufactured by Asahi Kasei Corporation); FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D, or 222D (manufactured by Neos Corporation). In addition, as the silicon-based surfactant, a polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical co., ltd.) may also be used.
In addition to the known surfactants described above, the surfactant may be synthesized using a fluorinated aliphatic compound produced by a modified polymerization (telomer) method (also referred to as a short chain polymer (telomer) method) or an oligomerization (oligomer) method (also referred to as an oligomer method). Specifically, a polymer having a fluoroaliphatic group derived from the fluoroaliphatic compound can be used as the surfactant. The fluoroaliphatic compound can be synthesized by a method described in, for example, japanese patent application laid-open No. 2002-90991.
The polymer having a fluoroaliphatic group is preferably a copolymer of a monomer having a fluoroaliphatic group and a (poly (alkylene oxide)) acrylate and/or a (poly (alkylene oxide)) methacrylate, and may be irregularly distributed or may be block-copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group and a poly (oxybutylene) group, and may be a unit having an alkylene group of a different chain length within the same chain length, such as a poly (oxyethylene, a block conjugate of oxypropylene and oxypropylene) or a poly (block conjugate of oxypropylene and oxypropylene). The copolymer of the monomer having a fluoroaliphatic group and the (poly (alkylene oxide)) acrylate (or methacrylate) may be not only a binary copolymer but also a ternary copolymer obtained by copolymerizing 2 or more different monomers having a fluoroaliphatic group and 2 or more different (poly (alkylene oxide)) acrylates (or methacrylates) at the same time.
Examples of the commercially available surfactants include Megaface F-178, F-470, F-473, F-475, F-476 and F-472 (manufactured by DIC CORPORATION) and have C 6 F 13 Copolymers of radical acrylates (or methacrylates) with (poly (alkylene oxide)) acrylates (or methacrylates), having C 3 F 7 Copolymers of acrylic (or methacrylic) esters of radicals, (poly (oxyethylene)) acrylic (or methacrylic) esters with (poly (oxypropylene)) acrylic (or methacrylic) esters.
Also, other than those described in U.S. patent application publication No. 2008/0248225 may be used
[0280] The surfactant other than fluorine-based and/or silicon-based surfactants described in the paragraph.
These surfactants may be used singly or in combination of 2 or more.
The content of the surfactant is preferably 0.0001 to 2.0% by mass, more preferably 0.0005 to 1.0% by mass, based on the total solid content of the composition.
< solvent >
A particular resist composition includes a solvent.
The solvent may be a solvent added alone, in addition to the 1 st solvent contained in the 1 st solution described below and the 2 nd solvent contained in the 2 nd solution described below.
The solvent preferably contains at least one of (M1) a propylene glycol monoalkyl ether carboxylate and (M2), and (M2) at least one member selected from the group consisting of propylene glycol monoalkyl ether, lactate, acetate, butyl butyrate, alkoxypropionate, chain ketone, cyclic ketone, lactone and alkylene carbonate. The solvent may contain components other than the components (M1) and (M2).
The present inventors have found that when such a solvent is used in combination with the above resin (a), the coatability of the composition is improved and a pattern having a small number of development defects can be formed. Although the reason for this is not clear, the present inventors considered that the reason for this is that the solvent has a good balance among solubility, boiling point and viscosity in the resin (a), and thus it is possible to suppress the unevenness of the film thickness of the composition film, the generation of precipitates during spin coating, and the like.
The component (M1) is preferably at least one selected from the group consisting of Propylene Glycol Monomethyl Ether Acetate (PGMEA), propylene glycol monomethyl ether propionate and propylene glycol monoethyl ether acetate, and more preferably Propylene Glycol Monomethyl Ether Acetate (PGMEA).
As the component (M2), the following are preferable.
As the propylene glycol monoalkyl ether, propylene Glycol Monomethyl Ether (PGME) or propylene glycol monoethyl ether (PGEE) is preferable.
The lactic acid ester is preferably ethyl lactate, butyl lactate or propyl lactate.
As the acetate, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate or 3-methoxybutyl acetate is preferred.
As alkoxypropionate, methyl 3-Methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferred.
As the chain ketone, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutanone, phenylpropione, methylethyl ketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetone alcohol (diacetoneylalcohol), acetomethanol, acetophenone, methylnaphthyl ketone or methylpentyl ketone is preferable.
The cyclic ketone is preferably methylcyclohexanone, isophorone or cyclohexanone.
As the lactone, gamma-butyrolactone is preferred.
As the alkylene carbonate, propylene carbonate is preferable.
As the component (M2), propylene Glycol Monomethyl Ether (PGME), ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, amyl acetate (pentayl acetate), γ -butyrolactone or propylene carbonate is more preferable, and Propylene Glycol Monomethyl Ether (PGME), ethyl lactate, cyclohexanone or γ -butyrolactone is more preferable.
In addition to the above components, an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, still more preferably 7 to 10) and 2 or less hetero atoms is preferably used.
The ester solvent having 7 or more carbon atoms and 2 or less hetero atoms is preferably amyl acetate (amyl acetate), 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, butyl butyrate or the like, and more preferably isoamyl acetate.
As the component (M2), a component having a flash point (hereinafter, also referred to as fp) of 37℃or higher is preferable. As such a component (M2), propylene glycol monomethyl ether (fp: 47 ℃ C.), ethyl lactate (fp: 53 ℃ C.), ethyl 3-ethoxypropionate (fp: 49 ℃ C.), methyl amyl ketone (fp: 42 ℃ C.), cyclohexanone (fp: 44 ℃ C.), amyl acetate (fp: 45 ℃ C.), methyl 2-hydroxyisobutyrate (fp: 45 ℃ C.), gamma-butyrolactone (fp: 101 ℃ C.), or propylene carbonate (fp: 132 ℃ C.) are preferable. Among them, propylene glycol monoethyl ether, ethyl lactate, amyl acetate or cyclohexanone are more preferable, and propylene glycol monoethyl ether or ethyl lactate are further preferable.
Here, "flash point" is a value described in a reagent product catalog of Tokyo Chemical Industry co., ltd. Or Sigma-Aldrich company.
The mixing mass ratio (M1/M2) of the component (M1) and the component (M2) in the mixed solvent is preferably in the range of "100/0" to "15/85", more preferably in the range of "100/0" to "40/60". With this configuration, the number of development defects can be further reduced.
As described above, the solvent may further contain components other than the components (M1) and (M2). In this case, the content of the components other than the components (M1) and (M2) is preferably in the range of 30 mass% or less, more preferably in the range of 5 to 30 mass%, relative to the total amount of the solvent.
The content of the solvent in the specific resist composition is preferably set to 0.5 to 30.0% by mass, more preferably 1.0 to 20.0% by mass, of the solid content concentration. Thus, the coatability of the specific resist composition is more excellent.
< other additives >)
The specific resist composition may further contain resins other than the above, crosslinking agents, acid growth agents, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors, dissolution accelerators, or the like.
[ method for producing resist composition ]
Next, a method of manufacturing the present invention will be described.
The manufacturing method of the present invention specifically includes a step A and a step B.
Step A: process for producing 1 st solution containing acid-decomposable resin and 1 st solvent
And (B) working procedure: a step of mixing the above solution 1 with a specific photoacid generator
Hereinafter, the steps a and B will be described.
< procedure A >)
The step A is a step of preparing a 1 st solution containing an acid-decomposable resin and a 1 st solvent. Hereinafter, the step of the step a (the method for producing the 1 st solution) will be described after the 1 st solution is described.
(solution 1)
The 1 st solution contains an acid-decomposable resin and a 1 st solvent.
As the acid-decomposable resin, as described above.
The 1 st solvent is not particularly limited, and examples thereof include solvents that can be contained in the resist composition (specifically, the component (M1) and the component (M2)), but propylene glycol monoalkyl ether carboxylate is preferable from the viewpoint of more excellent defect suppression of the formed pattern.
Specific examples of the propylene glycol monoalkyl ether carboxylate include Propylene Glycol Monomethyl Ether Acetate (PGMEA), propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate.
As the 1 st solvent, from the viewpoint that aggregation of the specific photoacid generator is further suppressed and defect suppression of the formed pattern is more excellent, among them, SP value is preferably less than 18.5MPa 1/2 。
The SP value of the present invention is calculated by the Fedors method described in "Properties of Polymers, second edition, 1976 publication". In addition, unless otherwise indicated, SP values are in units of MPa 1/2 。
In the propylene glycol monoalkyl ether carboxylate, the SP value is less than 18.5MPa 1/2 The propylene glycol monoalkyl ether carboxylate of (2) includes propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, and among these, propylene glycol monomethyl ether acetate is preferable.
The 1 st solvent may be used alone or in combination of 1 or more.
When plural kinds are used simultaneously as the 1 st solvent, it is preferable that at least 1 of the solvents has an SP value of less than 18.5MPa 1/2 More preferably less than 18.5MPa 1/2 。
The 1 st solution may contain other components than the acid-decomposable resin and the 1 st solvent, but preferably contains substantially no specific photoacid generator. Here, the "solution 1" contains substantially no specific photoacid generator. "means that the content of the specific photoacid generator is 3.0 mass% or less, preferably 2.0 mass% or less, more preferably 1.0 mass% or less, still more preferably 0.5 mass% or less, and particularly preferably 0.3 mass% or less, relative to the total mass of the 1 st solution. The lower limit value is 0 mass%.
The solution 1 preferably contains substantially no components other than the acid-decomposable resin and the solvent. Here, the "1 st solution substantially does not include any component other than the acid-decomposable resin and the solvent. "means that the total content of the other components excluding the acid-decomposable resin and the solvent is 3.0 mass% or less, preferably 2.0 mass% or less, more preferably 1.0 mass% or less, still more preferably 0.5 mass% or less, and particularly preferably 0.3 mass% or less, based on the total mass of the 1 st solution. The lower limit value is 0 mass%.
The solid content concentration of the 1 st solution is not particularly limited, but is, for example, 1.0 to 30.0 mass%, and is preferably 5.0 to 20.0 mass% from the viewpoint of further excellent defect suppression performance of the formed pattern. The solid content concentration is the mass percentage of the mass of the components other than the solvent with respect to the total mass of the 1 st solution.
(Process for producing the 1 st solution)
The method for producing the 1 st solution is not particularly limited, and it is preferable to mix the acid-decomposable resin and the 1 st solvent to the solid content concentration and then stir the mixture.
The stirring time is not particularly limited, but is preferably 1 hour or more, more preferably 5 hours or more. The longer the stirring time, the more preferable is, for example, 12 hours.
The stirring temperature is not particularly limited, but is preferably 15 to 25 ℃.
< procedure B >)
The step B is a step of mixing the 1 st solution with a specific photoacid generator.
The step B may be a step of directly mixing the specific photoacid generator with the 1 st solution (hereinafter also simply referred to as "step B1"), and preferably includes a step B2 and a step B3 from the viewpoint of further excellent defect suppression performance of the formed pattern. That is, it is preferable to prepare a solution in which a specific photoacid generator is dissolved in a solvent in advance, and mix the solution with the 1 st solution.
And a step B2: process for preparing solution 2 comprising specific photoacid generator and solvent 2
And step B3: a step of mixing the 1 st solution and the 2 nd solution
First, the steps of the step B1, the step of the step B2 (the method of producing the 2 nd solution), and the step of the step B3 will be described below.
(step of step B1)
The step B1 is a step of directly mixing a specific photoacid generator with the 1 st solution.
The step B1 is not particularly limited, and the obtained mixed solution is preferably stirred after directly mixing the solution 1 and the specific photoacid generator.
The stirring time is not particularly limited, but is preferably 1 hour or more, more preferably 5 hours or more. The longer the stirring time, the more preferable is, for example, 12 hours.
The stirring temperature is not particularly limited, but is preferably higher, preferably 10 ℃ or higher, from the viewpoint of further suppressing aggregation of the specific photoacid generator. The upper limit of the stirring temperature is preferably 40℃or less, from the viewpoint of suppressing deposition due to orientation change of the specific photoacid generator.
(solution 2)
The 2 nd solution contains a specific photoacid generator and a 2 nd solvent.
As specific photoacid generators, as described above.
The 2 nd solvent is not particularly limited, and examples thereof include solvents that can be contained in the resist composition (specifically, the component (M1) and the component (M2), etc.), and are preferably selected from the group consisting of propylene glycol monoalkyl ether, lactate, acetate, butyl butyrate, alkoxypropionate, chain ketone, cyclic ketone, lactone group and alkylene carbonate, from the viewpoint of more excellent defect-inhibiting property of the formed pattern.
As the propylene glycol monoalkyl ether, propylene Glycol Monomethyl Ether (PGME) or propylene glycol monoethyl ether (PGEE) is preferable.
The lactic acid ester is preferably ethyl lactate, butyl lactate or propyl lactate.
As the acetate, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate or 3-methoxybutyl acetate is preferred.
As the alkoxypropionate, methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable.
As the chain ketone, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutanone, phenylpropione, methylethyl ketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetone alcohol (diacetoneylalcohol), acetomethanol, acetophenone, methylnaphthyl ketone or methylpentyl ketone is preferable.
The cyclic ketone is preferably methylcyclohexanone, isophorone or cyclohexanone.
As the lactone, gamma-butyrolactone is preferred.
As the alkylene carbonate, propylene carbonate is preferable.
As the 2 nd solvent, from the viewpoint of further suppressing the aggregation of the specific photoacid generator and further excellent defect suppression of the formed pattern, the SP value is preferably 18.5MPa 1/2 The above.
In the solvent, the SP value is 18.5MPa 1/2 The above solvents are preferably propylene glycol monomethyl ether, ethyl lactate, cyclohexanone, gamma-butyrolactone or propylene carbonate.
The 2 nd solvent may be used alone or in combination of 1 or more.
When plural kinds are used simultaneously as the 2 nd solvent, it is preferable that at least 1 kind of the solvents have SP value of 18.5MPa 1/2 The above are more preferably 18.5MPa 1/2 The above.
The 2 nd solvent is preferably a solvent having an SP value higher than that of the 1 st solvent contained in the 1 st solution, from the viewpoint of further suppressing aggregation of the specific photoacid generator and further excellent defect suppression of the formed pattern. In addition, when plural kinds of solvents are used simultaneously as the 1 st solvent and/or plural kinds of solvents are used simultaneously as the 2 nd solvent, it is preferable that all solvents corresponding to the 2 nd solvent have higher SP values than the solvents corresponding to the 1 st solvent.
As a specific combination of the 1 st solvent and the 2 nd solvent, the 1 st solvent preferably has an SP value of less than 18.5MPa 1/2 And the SP value of the 2 nd solvent is 18.5MPa 1/2 The above.
The 2 nd solution may contain other components than the specific photoacid generator and the 2 nd solvent, but preferably contains substantially no acid-decomposable resin. Here, the "solution 2" contains substantially no acid-decomposable resin. "means that the content of the acid-decomposable resin is 3.0 mass% or less, preferably 2.0 mass% or less, more preferably 1.0 mass% or less, still more preferably 0.5 mass% or less, and particularly preferably 0.3 mass% or less, relative to the total mass of the 2 nd solution. The lower limit value is 0 mass%.
The solution 2 preferably contains substantially no components other than the specific photoacid generator and solvent. Here, the "solution 2" contains substantially no components other than the specific photoacid generator and solvent. "means that the total content of the other components than the specific photoacid generator and solvent is 3.0 mass% or less, preferably 2.0 mass% or less, more preferably 1.0 mass% or less, still more preferably 0.5 mass% or less, and particularly preferably 0.3 mass% or less, based on the total mass of the 2 nd solution. The lower limit value is 0 mass%.
The solid content concentration of the solution 2 is not particularly limited, but is, for example, 1.0 to 30.0% by mass, preferably 5.0 to 30.0% by mass. In addition, the solid content concentration is a mass percentage of the mass of the component excluding the solvent with respect to the total mass of the 2 nd solution.
(method for producing solution 2)
The method for producing the 2 nd solution is not particularly limited, and it is preferable to mix the specific photoacid generator and the 2 nd solvent to the above solid concentration and then stir the mixture.
The stirring time is not particularly limited, but is preferably 1 hour or more, more preferably 5 hours or more. The longer the stirring time, the more preferable is, for example, 12 hours.
The stirring temperature is not particularly limited, but is preferably 15 to 25 ℃.
(step of step B3)
The step B3 is a step of mixing the 1 st solution and the 2 nd solution prepared in the step B2.
The method for mixing the 1 st solution and the 2 nd solution is not particularly limited.
Preferably, after the 1 st solution and the 2 nd solution are mixed, the obtained mixed solution is stirred.
The stirring time is not particularly limited, but is preferably 1 hour or more, more preferably 5 hours or more. The longer the stirring time, the more preferable is, for example, 12 hours.
The stirring temperature is not particularly limited, but is preferably higher, preferably 10 ℃ or higher, from the viewpoint of further suppressing aggregation of the specific photoacid generator. The upper limit of the stirring temperature is preferably 40℃or less, from the viewpoint of suppressing deposition due to orientation change of the specific photoacid generator.
< other Process (Process C) >)
The production method of the present invention may further include other steps (hereinafter also referred to as "step C").
An example of the production method of the present invention including the steps a, B, and C is shown below.
The amounts of the acid-decomposable resin, the specific photoacid generator, and the other components blended in the resist composition in the production method described below can be appropriately set according to the amounts of the target resist composition. As a preferable mode of the blending amount of each component in the resist composition, as described above.
(embodiment 1 of the production method)
The manufacturing method of embodiment 1 includes a step a, a step B1, and a step C1 described below. A resist composition was prepared through the process C1.
Step A: process for producing 1 st solution containing acid-decomposable resin and 1 st solvent
Step B1: directly mixing the above solution 1 with a specific photoacid generator
Step C1: a step of further mixing other components blended in the resist composition with the solution obtained at the time of step B1 and/or after the step B1
The steps a and B1 are as described above.
The other components blended in the resist composition are also as described above.
In step C1, the 1 st solvent used in step a is also preferable as the other component when the other component to be blended in the resist composition is further mixed with the solution obtained in step B1 and/or after the step B1. In step C1, when the 1 st solvent used in step a is further added to the solution obtained in step B1 and/or after step B1, the solid content concentration of the 1 st solution is preferably adjusted to 5.0 to 20.0 mass%. When the solid content concentration of the 1 st solution is 5.0 mass% or more, the solubility of the specific photoacid generator to the 1 st solvent is further improved because the concentration of the acid-decomposable resin is high (i.e., the presence rate in the solution is high), and the defect suppression property of the formed pattern is more excellent. On the other hand, when the solid content concentration of the 1 st solution is 20.0 mass% or less, aggregation of the acid-decomposable resin in the 1 st solution is further suppressed, and defect suppression of the formed pattern is more excellent.
(embodiment 2 of the production method)
The manufacturing method of embodiment 2 includes a step a, a step B2, a step B3, and a step C2 described below. The resist composition was prepared through the process C2.
Step A: process for producing 1 st solution containing acid-decomposable resin and 1 st solvent
And a step B2: process for preparing solution 2 comprising specific photoacid generator and solvent 2
And step B3: a step of mixing the 1 st solution and the 2 nd solution
Step C2: a step of further mixing other components blended in the resist composition with the solution obtained through the step B3 (hereinafter also referred to as "solution 3")
The steps a, B2 and B3 are as described above.
Further, the 2 nd solvent preferably has a higher SP value than the 1 st solvent. SP values for the 1 st and 2 nd solvents are as described above.
The other components blended in the resist composition are also as described above. In addition, when other components to be blended in the resist composition are further mixed with the solution obtained in the step C2 and/or the solution obtained in the step B3, the 1 st solvent used in the step a is also preferable as the other components. When the 1 st solvent used in step a is further added to the solution obtained in step C2 and/or through step B3, the solid content concentration of the 1 st solution is preferably adjusted to 5.0 to 20.0 mass%. When the solid content concentration of the 1 st solution is 5.0 mass% or more, the solubility of the specific photoacid generator to the 1 st solvent is further improved because the concentration of the acid-decomposable resin is high (i.e., the presence rate in the solution is high), and the defect suppression property of the formed pattern is more excellent. On the other hand, when the solid content concentration of the 1 st solution is 20.0 mass% or less, aggregation of the acid-decomposable resin in the 1 st solution is further suppressed, and defect suppression of the formed pattern is more excellent.
From the viewpoint of more excellent defect suppression of the formed pattern, embodiment 2 of the production method preferably satisfies the following condition T1 (preferably the following condition T2).
Condition T1: comprises a step A, a step B2', a step B3 and a step C2 described below.
Step A: process for producing 1 st solution containing acid-decomposable resin and 1 st solvent
Procedure B2': a step of preparing a 2 nd solution containing a specific photoacid generator and a 2 nd solvent having a higher SP value than the 1 st solvent
And step B3: a step of mixing the 1 st solution and the 2 nd solution
Step C2: a step of further mixing the solution obtained in the step B3 (solution 3) with other components blended in the resist composition
Condition T2: includes steps A ', B2', B3 and C2.
Procedure a': preparation of an acid-decomposable resin and an SP value of less than 18.5MPa 1/2 1 st solvent 1 st solution step
Procedure B2": preparation of a composition comprising the specified photoacid generator and having an SP value of 18.5MPa 1/2 The step of the 2 nd solution of the 2 nd solvent
And step B3: a step of mixing the 1 st solution and the 2 nd solution
Step C2: a step of further mixing the solution obtained in the step B3 (solution 3) with other components blended in the resist composition
(embodiment 3 of the production method)
The manufacturing method of embodiment 3 includes steps a ", B2, B3, and C3 described below. The resist composition was prepared through the process C3.
Procedure a ": a step of preparing a 1 st solution containing an acid-decomposable resin and a 1 st solvent, the 1 st solution having a solid content concentration of 5.0 to 20.0 mass%
And a step B2: process for preparing solution 2 comprising specific photoacid generator and solvent 2
And step B3: a step of mixing the 1 st solution and the 2 nd solution
Step C3: a step of further mixing the 1 st solvent and any other components blended in the resist composition with the solution obtained through the step B3 (hereinafter also referred to as "3 rd solution")
That is, the production method of embodiment 3 is a method of producing a resist composition by further mixing the 1 st solvent (and any other components constituting the resist composition) with the 3 rd solution obtained by mixing the 1 st solution and the 2 nd solution having a solid content concentration of 5.0 to 20.0 mass%.
When the solid content concentration of the 1 st solution is 5.0 mass% or more, the concentration of the acid-decomposable resin is high (i.e., the presence rate in the solution is high), so that the solubility of the specific photoacid generator in the 1 st solvent is further improved in the step C3, and the defect suppression property of the formed pattern is further excellent. On the other hand, when the solid content concentration of the 1 st solution is 20.0 mass% or less, aggregation of the acid-decomposable resin in the 1 st solution is further suppressed, and defect suppression of the formed pattern is more excellent. That is, according to the manufacturing method of embodiment 3, the defect suppression performance of the formed pattern is more excellent.
The steps B2 and B3 are as described above.
Further, the 2 nd solvent preferably has a higher SP value than the 1 st solvent. SP values for the 1 st and 2 nd solvents are as described above.
The other components blended in the resist composition are also as described above.
The step C3 is preferably a step of further mixing the 1 st solvent and other components blended in the resist composition with the solution (3 rd solution) obtained through the step B3.
From the viewpoint of more excellent defect suppression of the formed pattern, embodiment 3 of the manufacturing method preferably satisfies the following condition T3.
Condition T3: includes a step A '", a step B2", a step B3 and a step C3' described below.
Procedure a' ": preparation of an acid-decomposable resin and an SP value of less than 18.5MPa 1/2 1 st solvent of (2), and a solid content concentration of 5.0 to 20.0 mass%
Procedure B2": preparation of a composition comprising the specified photoacid generator and having an SP value of 18.5MPa 1/2 The step of the 2 nd solution of the 2 nd solvent
And step B3: a step of mixing the 1 st solution and the 2 nd solution
Procedure C3': a step of further mixing the 1 st solvent and other components blended in the resist composition with the solution (3 rd solution) obtained through the step B3
Purification treatment and preservation method
In the production method of the present invention, the resist composition having undergone the above-described step a, step B and optional step C is preferably filtered using a plurality of filters having different materials (may be circulated filtration). For example, it is preferable to sequentially connect a polyethylene filter having a pore diameter of 50nm, a nylon filter having a pore diameter of 10nm, and a polyethylene filter having a pore diameter of 3 to 5nm to filter. The filtration is preferably carried out by circulating the filtration more than 2 times. In addition, the filtering step has the effect of reducing the content of metal impurities in the composition. The smaller the pressure difference between the filters, the better, usually 0.1MPa or less, preferably 0.05MPa or less, more preferably 0.01MPa or less. The smaller the pressure difference between the filter and the filling nozzle is, the better, and is usually 0.5MPa or less, preferably 0.2MPa or less, and more preferably 0.1MPa or less.
Further, as a method of performing cyclic filtration using a filter in the production of a resist composition, a method of performing cyclic filtration 2 or more times using a polytetrafluoroethylene filter having a pore size of 50nm, for example, is also preferable.
Further, the inside of the apparatus for producing a resist composition is preferably replaced with an inert gas such as nitrogen. This can inhibit the dissolution of the reactive gas such as oxygen into the resist composition.
After the resist composition was filtered through a filter, it was filled in a cleaning vessel. Preferably, the resist composition filled in the container is stored refrigerated. Thus, deterioration of performance with time is suppressed. The shorter the time from the completion of filling the resist composition into the container to the start of cold storage, the more preferable is, usually, 24 hours or less, preferably 16 hours or less, more preferably 12 hours or less, and still more preferably 10 hours or less. The storage temperature is preferably 0 to 15 ℃, more preferably 0 to 10 ℃, still more preferably 0 to 5 ℃.
In the resist composition produced by the production method of the present invention, the content of metal atoms is preferably reduced.
Hereinafter, a specific example of a method for reducing the content of metal atoms in the resist composition will be described.
As a method for reducing the content of metal atoms in the resist composition, for example, a method of adjustment by filtration using a filter can be cited. The pore size of the filter is preferably less than 100nm, more preferably 10nm or less, and even more preferably 5nm or less. The filter is preferably a polytetrafluoroethylene filter, a polyethylene filter, or a nylon filter. The filter may be constructed of a composite material that combines the filter raw materials described above and an ion exchange medium. The filter may be a filter which has been previously washed with an organic solvent. In the filter filtration step, a plurality of filters may be connected in series or in parallel to use the filter. When a plurality of filters are used, filters having different pore diameters and/or materials may be used in combination. The various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a cyclic filtering step.
Examples of the method for reducing the metal atom content in the resist composition include a method of selecting a raw material having a small metal content as a raw material constituting each material in the resist composition, a method of filtering a raw material constituting each material in the resist composition by a filter, and a method of distilling an apparatus by lining the inside of the apparatus with teflon (registered trademark) or the like while suppressing contamination as much as possible.
In addition, as a method for reducing the metal atom content in the resist composition, the metal atom content may be removed by an adsorbent in addition to the above-mentioned filter filtration, or a combination of the filter filtration and the adsorbent may be used. As the adsorbent, a known adsorbent can be used, and for example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
In addition, in order to reduce the metal atom content in the resist composition, it is necessary to prevent the mixing of metal impurities in the manufacturing process. It is possible to confirm whether or not the metal impurities are sufficiently removed from the manufacturing apparatus by measuring the content of the metal component contained in the cleaning liquid used when cleaning the manufacturing apparatus.
[ use ]
The resist composition obtained by the production method of the present invention corresponds to a resist composition which reacts and changes in properties by irradiation with actinic rays or radiation. More specifically, the resist composition obtained by the production method of the present invention relates to a resist composition used in a semiconductor production process such as IC (Integrated Circuit: integrated circuit), production of a circuit board such as liquid crystal or thermal head, production of a mold structure for imprinting, other photolithography processing processes, or production of a lithographic printing plate or an acid-curable composition.
The pattern formed in the present invention can be used in an etching process, an ion implantation process, a bump electrode forming process, a rewiring forming process, MEMS (Micro Electro Mechanical Systems: microelectromechanical system), and the like.
[ method of Forming Pattern ]
The pattern forming method of the present invention includes the following steps 1 to 3.
Step 1: a step of forming a resist film on a support (on a substrate) using the resist composition obtained by the production method of the present invention
Step 2: exposing the resist film
And step 3: developing the exposed resist film with a developer
The steps of the above steps will be described in detail below.
[ Process 1: resist film Forming Process
Step 1 is a step of forming a resist film on a support (on a substrate) using a resist composition. As a method for forming a resist film on a substrate using the resist composition, a method of applying the resist composition to a substrate is exemplified.
The resist composition can be coated on a substrate (e.g., silicon dioxide coating) used in the manufacture of, for example, integrated circuit elements by a suitable coating method such as a spin coater or coater. As the coating method, spin coating using a spin coater is preferable. The rotation speed in spin coating using a spin coater is preferably 1000 to 3000rpm.
The substrate may be dried to form a resist film after the resist composition is applied. In addition, various base films (inorganic films, organic films, antireflection films) may be formed on the lower layer of the resist film as needed.
As a drying method, a method of drying by heating is exemplified. The heating may be performed by a device provided in a general exposure machine and/or development machine, or may be performed by using a hot plate or the like. The heating temperature is preferably 80 to 150 ℃, more preferably 80 to 140 ℃, and still more preferably 80 to 130 ℃. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and still more preferably 60 to 600 seconds.
The thickness of the resist film is not particularly limited, but is preferably 10 to 150nm, more preferably 15 to 100nm, from the viewpoint of enabling formation of a fine pattern with higher accuracy.
In addition, a top coat layer may be formed on top of the resist film using the top coat composition.
It is preferable that the top coat composition can be further uniformly coated on the upper layer of the resist film without mixing with the resist film.
And, the resist film is preferably dried before the formation of the top coat layer. Next, a top coat composition is applied on the obtained resist film by the same method as the above-described resist film forming method, and further dried, whereby a top coat layer can be formed.
The film thickness of the top coat is preferably 10 to 200nm, more preferably 20 to 100nm.
The top coat composition comprises, for example, a resin, additives, and a solvent.
As the resin, the same resin as the hydrophobic resin can be used. The content of the resin is preferably 50 to 99.9 mass%, more preferably 60 to 99.7 mass%, relative to the total solid content of the top coat composition.
As the above-mentioned additive, the above-mentioned acid diffusion controlling agent can be used. Also, compounds having a radical trapping group such as a compound containing an N-oxy radical may be used. Examples of such a compound include [4- (benzoyloxy) -2, 6-tetramethylpiperidinooxy ] radicals. The content of the additive is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, relative to the total solid content of the top coat composition.
The solvent is preferably insoluble in the resist film, and examples thereof include an alcohol-based solvent (e.g., 4-methyl-2-pentanol), an ether-based solvent (e.g., diisoamyl ether), an ester-based solvent, a fluorine-based solvent, and a hydrocarbon-based solvent (e.g., n-decane).
The content of the solvent in the top coat composition is preferably set to a solid content concentration of 0.5 to 30 mass%, more preferably 1 to 20 mass%.
The top coat composition may contain a surfactant in addition to the above-mentioned additives, and as the surfactant, the same surfactant as that which may be contained in the resist composition may be used. The content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, relative to the total solid content of the top coat composition.
The top coat layer is not particularly limited, and a conventionally known top coat layer can be formed by a conventionally known method, and for example, the top coat layer can be formed based on the descriptions in paragraphs [0072] to [0082] in Japanese patent application laid-open No. 2014-059543.
For example, it is preferable to form a top coat layer containing an alkaline compound as described in japanese patent application laid-open No. 2013-61648 on a resist film. Specific examples of the basic compound that the topcoat layer can contain include the basic compounds that the resist composition can contain.
And, the top coat layer preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.
[ Process 2: exposure process
The step 2 is a step of exposing the resist film.
As a method of exposure, a method of irradiating a formed resist film with actinic rays or radiation through a predetermined mask is exemplified.
Examples of the actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays and electron beams, and the wavelength is preferably 250nm or less, more preferably 220nm or less, particularly preferably 1 to 200Examples of the extreme ultraviolet light at nm include KrF excimer laser (248 nm), arF excimer laser (193 nm), and F 2 Excimer laser (157 nm), EUV (13 nm), X-rays, and electron beams.
Baking (heating) is preferably performed before development is performed after exposure. The response of the exposed portion is promoted by baking, and the sensitivity and pattern shape become more excellent.
The heating temperature is preferably 80 to 150 ℃, more preferably 80 to 140 ℃, and still more preferably 80 to 130 ℃.
The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and still more preferably 30 to 120 seconds.
The heating may be performed by a device provided in a general exposure machine and/or development machine, or may be performed by using a hot plate or the like.
This process is also called post exposure bake.
[ procedure 3: development process
The step 3 is a step of developing the exposed resist film with a developer to form a pattern.
As a developing method, there may be mentioned: a method of immersing the substrate in a tank filled with a developer for a certain period of time (dip method); a method (spin immersion method) in which a developer is raised on the surface of a substrate by surface tension and left for a predetermined period of time to develop; a method of spraying a developer solution onto a substrate surface (spray method); and a method (dynamic dispense method, dynamic dispensing method) of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed.
After the development step, a step of stopping development while replacing it with another solvent may be performed.
The development time is not particularly limited as long as the resin in the unexposed portion is sufficiently dissolved, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
The temperature of the developing solution is preferably 0 to 50 ℃, more preferably 15 to 35 ℃.
As the developer, an alkaline developer and an organic solvent developer can be mentioned.
The alkaline developer preferably uses an aqueous alkali solution containing an alkali. The type of the aqueous alkali solution is not particularly limited, and examples thereof include aqueous alkali solutions containing quaternary ammonium salts typified by tetramethylammonium hydroxide, inorganic bases, primary amines, secondary amines, tertiary amines, alcohol amines, cyclic amines, and the like. Among them, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt typified by tetramethylammonium hydroxide (TMAH). An appropriate amount of alcohol, surfactant, or the like may be added to the alkaline developer. The alkali concentration of the alkali developer is usually 0.1 to 20 mass%. The pH of the alkaline developer is usually 10.0 to 15.0.
The organic solvent developer refers to a developer containing an organic solvent.
The vapor pressure of the organic solvent (vapor pressure as a whole when the solvent is a mixed solvent) contained in the organic solvent developer at 20 ℃ is preferably 5kPa or less, more preferably 3kPa or less, and further preferably 2kPa or less. By setting the vapor pressure of the organic solvent to 5kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer plane is improved, with the result that the dimensional uniformity in the wafer plane is improved.
The organic solvent used in the organic solvent developer may be a known organic solvent, and examples thereof include an ester-based solvent, a ketone-based solvent, an alcohol-based solvent, an amide-based solvent, an ether-based solvent, and a hydrocarbon-based solvent.
When EUV and electron beams are used in the exposure step, from the viewpoint of suppressing swelling of the resist film, an ester-based solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, still more preferably 7 to 10) and 2 or less heteroatoms is preferably used as the organic solvent contained in the organic solvent developer.
The hetero atom of the ester solvent is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and the like. The number of heteroatoms is preferably 2 or less.
The ester-based solvent having 7 or more carbon atoms and 2 or less hetero atoms is preferably amyl acetate (pentayl acetate), isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, amyl propionate, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, butyl butyrate or the like, and more preferably isoamyl acetate.
When EUV and electron beam are used in the exposure step, a mixed solvent of the ester-based solvent and the hydrocarbon-based solvent or a mixed solvent of the ketone-based solvent and the hydrocarbon-based solvent may be used in place of the ester-based solvent having 7 or more carbon atoms and 2 or less hetero atoms in the organic solvent contained in the organic solvent developer. In this case, it is also effective to suppress swelling of the resist film.
When the ester-based solvent is used in combination with the hydrocarbon-based solvent, isoamyl acetate is preferably used as the ester-based solvent. The hydrocarbon solvent is preferably a saturated hydrocarbon solvent (for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.) from the viewpoint of adjusting the solubility of the resist film.
When the ketone solvent is used in combination with the hydrocarbon solvent, 2-heptanone is preferably used as the ketone solvent. The hydrocarbon solvent is preferably a saturated hydrocarbon solvent (for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.) from the viewpoint of adjusting the solubility of the resist film.
When the above mixed solvent is used, the content of the hydrocarbon-based solvent depends on the solvent solubility of the resist film, and thus is not particularly limited, and the required amount may be determined by appropriately preparing.
The organic solvent may be mixed with a plurality of solvents, or may be mixed with a solvent other than the above or water. However, in order to sufficiently exhibit the effects of the present invention, the water content of the entire developer is preferably less than 10% by mass, and more preferably substantially no water content is contained. The concentration of the organic solvent (in total when a plurality of the organic solvents are mixed) in the developer is preferably 50% by mass or more, more preferably 50 to 100% by mass, still more preferably 85 to 100% by mass, particularly preferably 90 to 100% by mass, and most preferably 95 to 100% by mass.
[ other procedures ]
The pattern forming method preferably includes a step of cleaning with a rinse solution after the step 3.
The rinse liquid used in the rinsing step after the step of developing with the developer is, for example, pure water. In addition, a surfactant may be added to pure water in an appropriate amount.
The rinse solution may be added with a surfactant in an appropriate amount.
The method of the rinsing step is not particularly limited, and examples thereof include a method of continuously spraying a rinse solution onto a substrate rotating at a constant speed (spin coating method), a method of immersing the substrate in a tank filled with the rinse solution for a constant time (immersion method), and a method of spraying the rinse solution onto the surface of the substrate (spray method).
Further, the pattern forming method of the present invention may include a heating process (Post Bake) after the rinsing process. The developer and rinse liquid remaining between the patterns and inside the patterns by baking can be removed by this step. Further, this step has an effect of smoothing the resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is usually carried out at 40 to 250 ℃ (preferably 90 to 200 ℃), usually for 10 seconds to 3 minutes (preferably 30 to 120 seconds).
Further, the etching process of the substrate may be performed using the formed pattern as a mask. That is, the pattern formed in step 3 may be used as a mask, and the substrate (or the underlayer film and the substrate) may be processed to form a pattern on the substrate.
The method of processing the substrate (or the underlayer film and the substrate) is not particularly limited, and a method of forming a pattern on the substrate by dry etching the substrate (or the underlayer film and the substrate) using the pattern formed in step 3 as a mask is preferable.
The dry etching may be 1-stage etching or etching composed of a plurality of stages. When the etching is an etching composed of a plurality of stages, the etching of each stage may be the same or different.
The etching may be performed by any known method, and various conditions and the like are appropriately determined according to the type, use, and the like of the substrate. For example, etching may be performed in accordance with the international optical engineering institute (The International Society for Optical Engineering) agency of sci (proc. Of SPIE) vol.6924, 692420 (2008), japanese patent application laid-open No. 2009-267112, or the like. And, the publisher may also be published as in "semiconductor technology textbook fourth edition 2007: the method described in "chapter 4 etching" of SEMI japan.
Among them, oxygen plasma etching is preferable as the dry etching.
Among various materials other than the resist composition used in the pattern forming method of the present invention (for example, developer, rinse solution, anti-reflective coating forming composition, top coat forming composition, etc.), the smaller the amount of impurities such as metal (for example, na, K, ca, fe, cu, mg, al, li, cr, ni, sn, ag, as, au, ba, cd, co, pb, ti, V, W, zn, etc.) is, the better. The content of impurities contained in these materials is preferably 1 mass ppm or less, for example.
As a method for reducing impurities such as metals in various materials other than the resist composition, filtration using a filter is exemplified. The pore size of the filter is preferably less than 100nm, more preferably 10nm or less, and even more preferably 5nm or less. The filter is preferably a polytetrafluoroethylene filter, a polyethylene filter, or a nylon filter. The filter may be constructed of a composite material that combines the filter raw materials described above and an ion exchange medium. The filter may be a filter which has been previously washed with an organic solvent. In the filter filtration step, a plurality of filters may be connected in series or in parallel to use the filter. When a plurality of filters are used, filters having different pore diameters and/or materials may be used in combination. The various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a cyclic filtering step.
Examples of the method for reducing impurities such as metals in various materials other than the resist composition include a method for selecting a raw material having a small metal content as a raw material constituting the various materials, a method for filtering a raw material constituting the various materials by a filter, and a method for distilling the raw material by lining the inside of the apparatus with teflon (registered trademark) or the like while suppressing contamination as much as possible.
In addition, as a method for reducing impurities such as metals in various materials other than the resist composition, impurities may be removed by an adsorbent in addition to the above-described filter filtration, or a combination of filter filtration and adsorbent may be used. As the adsorbent, a known adsorbent can be used, and for example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used. In order to reduce impurities such as metals contained in various materials other than the resist composition, it is necessary to prevent the mixing of metal impurities in the manufacturing process. It is possible to confirm whether or not the metal impurities are sufficiently removed from the manufacturing apparatus by measuring the content of the metal component contained in the cleaning liquid used when cleaning the manufacturing apparatus.
In order to prevent failures of chemical liquid piping and various components (filters, O-rings, hoses, etc.) caused by electrostatic discharge accompanied by electrification of static electricity, the organic treatment liquid such as a rinse liquid may be added with a conductive compound. The conductive compound is not particularly limited, and examples thereof include methanol. The amount to be added is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of maintaining preferable development characteristics or rinsing characteristics.
As the chemical liquid piping, various piping coated with SUS (stainless steel) or polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, or the like) subjected to antistatic treatment can be used. Similarly, as for the filter and the O-ring, polyethylene, polypropylene, or a fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, or the like) subjected to antistatic treatment can be used.
The method of improving the surface roughness of a pattern can be applied to a pattern formed by the pattern forming method of the present invention. As a method for improving the surface roughness of the pattern, for example, a method of treating the pattern with a plasma of a hydrogen-containing gas as disclosed in international publication No. 2014/002808 is given. In addition, known methods described in, for example, japanese patent application laid-open No. 2004-235468, U.S. patent application publication No. 2010/0020297, japanese patent application laid-open No. 2008-83084, and Proc.of SPIE Vol.8328 83280N-1"EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement" are also included.
When the formed pattern is linear, the aspect ratio obtained by dividing the pattern height by the line width is preferably 2.5 or less, more preferably 2.1 or less, and even more preferably 1.7 or less.
When the pattern to be formed is a trench (groove) pattern or a contact hole pattern, the aspect ratio obtained by dividing the pattern height by the trench width or the aperture is preferably 4.0 or less, more preferably 3.5 or less, and even more preferably 3.0 or less.
The pattern forming method of the present invention can also be used for guide pattern formation in DSA (Directed Self-Assembly) (for example, refer to ACS Nano vol.4No. 8-4815-4823).
Further, the pattern formed by the above method can be used as a core of a Spacer Process (Spacer Process) disclosed in, for example, japanese patent application laid-open publication No. 3-270227 and japanese patent application laid-open publication No. 2013-164509.
[ method of manufacturing electronic device ]
The present invention also relates to a method for manufacturing an electronic device including the above-described pattern forming method. Examples of the electronic device include electronic devices that can be mounted on electric and electronic equipment (home appliances, OA (Office Automation, office automation), media-related equipment, optical equipment, communication equipment, and the like).
Examples
The present invention will be described in further detail with reference to examples. The materials, amounts of use, proportions, processing contents, processing steps, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the examples shown below.
[ production of actinic-ray-sensitive or radiation-sensitive resin composition (resist composition) ]
Hereinafter, the various components to be blended in the resist composition will be described first.
[ preparation of solution 1 ]
The following describes the 1 st solution shown in table 4 and table 7.
Table 2 shows the 1 st solutions (X-1 to X-22) shown in Table 4 and Table 7.
The following describes the method of producing the 1 st solution, after explaining the various components contained in the 1 st solution shown in table 2.
< ingredients >
(acid-decomposable resin (resin A))
The resins A (resins A-1 to A-16) shown in Table 2 are shown below.
The resins A-1 to A-16 were synthesized according to the method for synthesizing the resin A-1 (Synthesis example 1) described later. The composition ratio (molar ratio; corresponding in order from left to right), weight average molecular weight (Mw) and dispersity (Mw/Mn) of each repeating unit described later are shown in Table 1.
The weight average molecular weights (Mw) and the dispersity (Mw/Mn) (in terms of polystyrene) of the resins A-1 to A-16 were measured by GPC (carrier: tetrahydrofuran (THF)). And, by 13 The composition ratio (mol%) of the resin was measured by C-NMR (nuclear magnetic resonance ).
TABLE 1
The structural formulas of the resins A-1 to A-16 shown in Table 1 are shown below.
[ chemical formula 70]
[ chemical formula 71]
Synthesis example 1: synthesis of resin A-1
Cyclohexanone (113 g) was heated to 80 ℃ under a nitrogen flow. While stirring the solution, a mixed solution of a monomer represented by the following formula M-1 (25.5 g), a monomer represented by the following formula M-2 (31.6 g), cyclohexanone (210 g) and dimethyl 2,2' -azobisisobutyrate [ V-601, manufactured by FUJIFILM Wako Pure Chemical Corporation ] (6.21 g) was added dropwise over 6 hours to obtain a reaction solution. After completion of the dropwise addition, the reaction solution was further stirred at 80℃for 2 hours. The obtained reaction solution was naturally cooled, reprecipitated with a large amount of methanol/water (mass ratio 9:1), and then filtered, and the obtained solid was dried in vacuo to obtain 52g of resin A-1.
[ chemical formula 72]
The weight average molecular weight (Mw: in terms of polystyrene) obtained from GPC (carrier: tetrahydrofuran (THF)) of the obtained resin A-1 was 6500, and the dispersity (Mw/Mn) was 1.52. By passing through 13 The composition ratio by C-NMR (nuclear magnetic resonance ) was 50/50 in terms of molar ratio.
(solvent 1)
The 1 st solvents (solvents C-1 to C-3) shown in Table 2 are shown below.
C-1: propylene glycol monomethyl ether acetate (PGMEA, SP value: 17.9 MPa) 1/2 )
C-2: 2-heptanone (SP value: 18.1 MPa) 1/2 )
C-3: cyclohexanone (SP value: 20.0 MPa) 1/2 )
< preparation of solution 1 >
The resin (A) and the 1 st solvent were mixed so as to have the solid content concentrations shown in Table 2, and stirred for 6 hours to prepare 1 st solutions (solutions X-1 to X-22). In addition, in the 1 st solution, the solid component represents all components except the solvent.
TABLE 2
[ preparation of solution 2]
The following describes the 2 nd solutions shown in tables 4 and 7.
Table 3 shows the 2 nd solutions (Y-1 to Y-24, YY-1 and YY-2) shown in Table 4 and Table 7.
The following describes the method of producing the 2 nd solution after the explanation of the various components contained in the 2 nd solution shown in Table 3.
< ingredients >
(specific photoacid generator)
The structures of specific photoacid generators B (compounds B-1 to B-24) shown in Table 3 are shown below. The compounds B-1 to B-18 and B-21 to B-24 correspond to the above-mentioned compound (I), the compound B-20 corresponds to the above-mentioned compound (II), and the compound B-19 corresponds to the above-mentioned compound (III).
[ chemical formula 73]
[ chemical formula 74]
[ chemical formula 75]
(solvent 2)
The 2 nd solvents (solvents D-1 to D-6) shown in Table 3 are shown below.
D-1: propylene glycol monomethyl etherEther (PGME, SP value: 23.0MPa for short) 1/2 )
D-2: cyclohexanone (SP value: 20.0 MPa) 1/2 )
D-3: gamma-butyrolactone (SP value: 23.8 MPa) 1/2 )
D-4: ethyl lactate (SP value: 24.4 MPa) 1/2 )
D-5: propylene glycol monomethyl ether acetate (PGMEA, SP value: 17.9 MPa) 1/2 )
D-6: 2-heptanone (SP value: 18.1 MPa) 1/2 )
< preparation of solution 2 >
The 2 nd solution (solutions Y-1 to Y-24, YY-1 and YY-2) was prepared by mixing the specific photoacid generator and the 2 nd solvent so as to have the solid content concentrations shown in Table 3 and stirring for 6 hours. In addition, in the 2 nd solution, the solid component represents all components except the solvent. In addition, in the solutions Y-7 and Y-9 in Table 3, the solvent ratio represents the mass ratio.
TABLE 3
[ resin (A) ]
As the resins (A) (A-1, A-3, A-5, A-8, A-9, A-11) shown in tables 4 and 7, the resins A-1, A-3, A-5, A-8, A-9 and A-11 were used in column [ preparation of solution 1 ].
[ specific photoacid generator ]
As specific photoacid generators (B-2, B-3, B-5, B-10, B-12 and B-20) shown in tables 4 and 7, the photoacid generators B-2, B-3, B-5, B-10, B-12 and B-20 described above were used in column [ preparation of solution 2 ].
[ acid diffusion controlling agent ]
The structures of the acid diffusion control agents (N-1 to N-7) shown in Table 4 and Table 7 are shown below.
[ chemical formula 76]
[ hydrophobic resin ]
The structures of the hydrophobic resins E (compounds E-1 to E-6) shown in Table 4 are shown below. In addition, the numerical value of each repeating unit represents a molar ratio.
[ chemical formula 77]
[ chemical formula 78]
[ additional solvent addition ]
As the additional solvents (C-1 to C-3) shown in tables 4 and 7, the above-mentioned solvents C-1 to C-3 were used in column [ preparation of solution 1 ].
As the additional solvents (D-1 to D-6) shown in Table 4 and Table 7, the above-mentioned 2 nd solvents D-1 to D-6 were used in column [ preparation of 2 nd solution ].
The surfactants (H-1 to H-3) shown in Table 7 are shown below.
"H-1": megaface F176 (fluorine-based surfactant manufactured by DIC CORPORATION)
"H-2": megafacer08 (DIC CORPORATION, fluorine-based and silicon-based surfactant) "H-3": PF656 (OMNOVA Solutions Inc. manufactured and fluorine-based surfactant)
[ preparation of resist composition for ArF Exposure ]
The components shown in table 4 were mixed so that the solid content concentration became 4 mass% by the mixing method shown in table. The obtained mixture was filtered in this order with a nylon filter having a pore size of 5nm, a polyethylene filter having a pore size of 3nm, and a polyethylene filter having a pore size of 1nm, to prepare a resist composition for ArF exposure. The solid component herein means all components except the solvent.
The blending methods shown in tables 4 and 7 are shown below.
"preparation method 1 (corresponding to" 1 "in the column" preparation method "in tables 4 and 7") ": the solution obtained by mixing the 1 st solution and the 2 nd solution was mixed with the 1 st solvent and other components shown in tables 4 and 7, and blended. In the case of the resist composition Re-2, for example, the 1 st solvent to be added is C-1 (see column "additional solvent 1" in Table 4), which corresponds to the 1 st solvent (solvent C-1) contained in the solution X-2 as the 1 st solution.
"preparation method 2 (corresponding to" 2 "in the column" preparation method "in tables 4 and 7") ": the solutions obtained by mixing the 1 st solution and the 2 nd solution were mixed with other components shown in tables 4 and 7, and blended. In addition, in the preparation method 2, the additional addition of the 1 st solvent was not performed, and the solid content concentration of the 1 st solution was adjusted to be low.
"preparation method 3 (corresponding to" 3 "in the column" preparation method "in tables 4 and 7") ": the 1 st solution was directly added and mixed with a specific photoacid generator and other compounding ingredients shown in tables 4 and 7.
"preparation method 4 (corresponding to" 4 "in the column" preparation method "in tables 4 and 7") ": the resin (a), the specific photoacid generator, and other components shown in tables 4 and 7 were directly mixed and blended.
"preparation method 5 (corresponding to" 5 "in the column" preparation method "in table 4") ": the resin (a) and other components shown in tables 4 and 7 were directly added to the solution 2 and mixed.
Table 4 is shown below. In Table 5, the relationship among the resin (A), the specific photoacid generator, the 1 st solution, the 2 nd solution, and the additional solvent is shown collectively for each of the resist compositions Re-1 to Re-24 and Re-42 to Re-61.
In Table 5, in column "1 st solution-1" (and "1 st solution-2"), whether the SP value is less than 18.5MPa 1/2 "column 1 st solvent contained in 1 st solution-1 (and 1 st solution-2)SP value of less than 18.5MPa 1/2 The case of (C) is denoted by "A", and will be 18.5MPa 1/2 The above case is denoted by "B". In the column "whether the solid content concentration satisfies 5.0 to 20.0% by mass", the case where the solid content concentration of the 1 st solution-1 (and 1 st solution-2) satisfies 5.0 to 20.0% by mass is denoted by "A", and the case where the solid content concentration does not satisfy is denoted by "B".
In Table 5, in the column "solution 2-1" (and "solution 2-2"), whether the SP value is 18.5MPa or not 1/2 In the column above, the SP value of the 2 nd solvent contained in the 2 nd solution-1 (and the 2 nd solution-2) was 18.5MPa 1/2 The above case is denoted by "A" and will be less than 18.5MPa 1/2 The case of (2) is denoted by "B".
In table 5, the column "SP value of the 1 st solvent < SP value of the 2 nd solvent" indicates the magnitude relation between the SP value of the 1 st solvent contained in the 1 st solution and the SP value of the 2 nd solvent contained in the 2 nd solution. Specifically, the case where the relation of the SP value of the 1 st solvent < the SP value of the 2 nd solvent is satisfied is denoted by "a", and the case where the relation is not satisfied is denoted by "B".
In Table 5, in the column "whether or not the 1 st solvent is contained as the additional solvent", the case where the 1 st solvents C-1 to C-3 are contained in the additional solvent is denoted by "A", and the case where the additional solvent is not contained is denoted by "B".
TABLE 4
TABLE 5
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[ preparation of Top coating composition ]
The following resin PT-1 (10 g), the following additive DT-1 (1.3 g), and the following additive DT-2 (0.06 g) were mixed with the solvent 4-methyl-2-pentanol (MIBC)/n-decane=70/30 (mass%) so that the solid content concentration became 3 mass%. Next, the resulting mixture was filtered in this order with a polyethylene filter having a pore size of 50nm, a nylon filter having a pore size of 10nm, and a polyethylene filter having a pore size of 5nm, to prepare a top coating composition. The solid component herein means all components except the solvent. The topcoat composition TC-1 obtained was used in the examples. In the resin PT-1 described below, the numerical value of each repeating unit represents a molar ratio.
[ chemical formula 79]
Pattern formation and defect evaluation: arF liquid immersion Exposure ]
[ Pattern formation and defect evaluation (1): arF liquid immersion exposure, alkali aqueous development ]
An antireflection film was formed by applying an organic antireflection film forming composition SOC9110D and an Si-containing antireflection film forming composition HM9825 on a silicon wafer. The obtained antireflective film was coated with an ArF exposure resist composition, and baked (PB: prebake (Prebake)) at 100℃for 60 seconds to form a resist film having a film thickness of 100nm, and in examples 5, 8, 10, 11, 13, 17, 20, 34, 36, 38, 40, 42, 52, 54, 56, 58, 60 and comparative example 4, a top coat composition TC-1 was formed on the resist film so that the film thickness became 100nm.
The obtained wafer was subjected to an ArF excimer laser immersion scanner (manufactured by ASML corporation; XT1700i, NA0.85, annular, outer sigma 0.9, inner sigma 0.6) and passed through a line width of 1 at 100 nm: the 1 line was exposed to a 6% halftone mask of the space pattern. Ultrapure water was used as the immersion liquid. Then, heating was performed at 90℃for 60 seconds (PEB: post Exposure Bake (post baking)). Next, immersed development was performed for 30 seconds as a developer in an aqueous tetramethylammonium hydroxide solution (2.38 mass%), and 1 of line width 100nm was formed by rinsing with pure water: 1 line and space pattern.
The obtained pattern wafer was inspected by using a defect evaluation device UVision5 manufactured by Applied Materials company, and a defect MAP was produced. Then, an image of the defect was obtained using semv ision G4 (manufactured by Applied Materials corporation), and the actual defect number of each silicon wafer was calculated. In addition, the actual defects generated in the pattern wafer are observed as images as shown in fig. 1 and 2, for example.
The actual defect number obtained was evaluated according to the following evaluation criteria. The smaller the number of defects, the better the result. The evaluation results are shown in table 6 below.
"S": the defect number is below 50
"A": the number of defects exceeds 50 and is less than 200
"B": the number of defects exceeds 200 and is 300 or less
"C": the number of defects exceeds 300 and is 400 or less
"D": the number of defects exceeds 400 and is less than 500
"E": the defect number exceeds 500
[ Pattern formation and defect evaluation (2): arF liquid immersion exposure, organic solvent development ]
Spin-on immersion development with butyl acetate as developer for 30 seconds and by rinsing with methyl isobutyl carbinol (MIBC) a line width of 1 at 100nm was formed: 1 line and space pattern, and the above [ pattern formation and defect evaluation (1): the ArF liquid immersion exposure and alkali aqueous solution development were carried out in the same manner to evaluate the number of defects in the pattern. The evaluation results are shown in table 6 below.
Table 6 is shown below.
In table 6, in the column of "pattern formation method", the term (1) means alkali aqueous solution development and the term (2) means organic solvent development.
TABLE 8
TABLE 6 Resist composition Top coat composition Pattern forming method Defects(s)
Example 1 Re-1 - (1) A
Example 2 Re-2 - (1) S
Example 3 Re-3 - (1) D
Example 4 Re-4 - (1) D
Example 5 Re-5 TC-1 (1) A
Example 6 Re-6 - (1) S
Example 7 Re-7 - (1) S
Example 8 Re-8 TC-1 (1) S
Example 9 Re-9 - (1) S
Example 10 Re-10 TC-1 (1) S
Example 11 Re-11 TC-1 (1) S
Example 12 Re-12 - (2) A
Example 13 Re-13 TC-1 (2) S
Example 14 Re-14 - (2) D
Example 15 Re-15 - (2) D
Example 16 Re-16 - (2) A
Example 17 Re-17 TC-1 (1) B
Example 18 Re-18 - (1) C
Example 19 Re-19 - (2) B
Example 20 Re-20 TC-1 (2) C
Comparative example 1 Re-21 - (1) E
Comparative example 2 Re-22 - (1) E
Comparative example 3 Re-23 - (2) E
Comparative example 4 Re-24 TC-1 (2) E
Example 34 Re-42 TC-1 (1) S
Example 35 Re-43 - (1) S
Example 36 Re-44 TC-1 (1) S
Example 37 Re-45 - (1) S
Example 38 Re-46 TC-1 (1) S
Example 39 Re-47 - (1) S
Example 40 Re-48 TC-1 (1) S
Example 41 Re-49 - (1) S
Example 42 Re-50 TC-1 (1) S
Example 43 Re-51 - (1) S
Example 44 Re-52 TC-1 (1) S
Example 45 Re-53 - (1) S
Example 46 Re-54 TC-1 (1) S
Example 47 Re-55 - (1) S
Example 48 Re-56 TC-1 (1) S
Example 49 Re-57 - (1) S
Example 50 Re-58 TC-1 (1) S
Example 51 Re-59 - (1) S
Example 52 Re-60 TC-1 (1) S
Example 53 Re-61 - (1) S
As is clear from the results of table 6, defects were suppressed according to the manufacturing method of examples. On the other hand, in the production method of the comparative example, it is found that the defect suppression property does not satisfy the desired requirement.
As is clear from the results of table 6, when the production method of the present invention satisfies the following condition T1 (preferably the following condition T2, more preferably the following condition T3), defects are further suppressed.
Condition T1: the manufacturing method of the present invention includes a step a, a step B2', a step B3, and a step C2 described below.
Step A: process for producing 1 st solution containing acid-decomposable resin and 1 st solvent
Procedure B2': a step of preparing a 2 nd solution containing a specific photoacid generator and a 2 nd solvent having a higher SP value than the 1 st solvent
And step B3: a step of mixing the 1 st solution and the 2 nd solution
Step C2: a step of further mixing the solution obtained in the step B3 (solution 3) with other components blended in the resist composition
Condition T2: the manufacturing method of the present invention includes steps a', B2", B3 and C2 described below.
Procedure a': preparation of the acid-decomposable resin containing the acid-decomposable resin and having an SP value of less than 18.5MPa 1/2 1 st solvent 1 st solution step
Procedure B2": preparation of a composition comprising the specified photoacid generator and having an SP value of 18.5MPa 1/2 The step of the 2 nd solution of the 2 nd solvent
And step B3: a step of mixing the 1 st solution and the 2 nd solution
Step C2: a step of further mixing the solution obtained in the step B3 (solution 3) with other components blended in the resist composition
Condition T3: the production method of the present invention includes a step A '", a step B2", a step B3, and a step C3' described below.
Procedure a' ": preparation of an acid-decomposable resin and an SP value of less than 18.5MPa 1/2 1 st solvent of (2), and a solid content concentration of 5.0 to 20.0 mass%
Procedure B2": preparation of a composition comprising the specified photoacid generator and having an SP value of 18.5MPa 1/2 The step of the 2 nd solution of the 2 nd solvent
And step B3: a step of mixing the 1 st solution and the 2 nd solution
Procedure C3': a step of further mixing the 1 st solvent and other components blended in the resist composition with the solution (3 rd solution) obtained through the step B3
In addition, the resist compositions Re-1 to Re-24-1 were prepared in the same manner as the respective preparation methods of the resist compositions Re-1 to Re-24 except that the acid diffusion control agent N-1 as a monovalent salt was used instead of the photoacid generator B as a polyvalent salt, and as a result, in the cases of the preparation methods 1 to 3 and the preparation methods 4 to 5, almost no difference in the defect suppression ability of the formed pattern was observed. When the acid diffusion control agent N-2, N-3 or N-4 was used in place of the acid diffusion control agent N-1, almost no difference in the defect suppressing ability of the formed pattern was observed between the cases of the preparation methods 1 to 3 and the preparation methods 4 to 5.
[ preparation of resist composition for EUV Exposure ]
The components shown in table 7 were mixed so that the solid content concentration became 1.3 mass%. The obtained mixture was filtered in this order with a nylon filter having a pore size of 5nm, a polyethylene filter having a pore size of 3nm, and a polyethylene filter having a pore size of 1nm, to prepare a resist composition for EUV exposure. The solid component as referred to herein means all components except the solvent.
The formulation methods shown in table 7 were as described above.
Table 7 is shown below. In Table 8, the relationship among the resin (A), the specific photoacid generator, the 1 st solution, the 2 nd solution, and the additional solvent is shown for each of the resist compositions Re-25 to Re-41.
In Table 8, in column "1 st solution-1" (and "1 st solution-2"), whether the "SP value is less than 18.5MPa 1/2 "in column, the SP value of the 1 st solvent contained in the 1 st solution-1 (and 1 st solution-2) is less than 18.5MPa 1/2 The case of (C) is denoted by "A", and will be 18.5MPa 1/2 The above case is denoted by "B". In the column "whether the solid content concentration satisfies 5.0 to 20.0% by mass", the case where the solid content concentration of the 1 st solution-1 (and 1 st solution-2) satisfies 5.0 to 20.0% by mass is denoted by "A", and the case where the solid content concentration does not satisfy is denoted by "B".
In Table 8, in the column "solution 2-1" (and "solution 2-2"), whether the SP value is 18.5MPa or not 1/2 In the column above, the SP value of the 2 nd solvent contained in the 2 nd solution-1 (and the 2 nd solution-2) was 18.5MPa 1/2 The above case is denoted by "A" and will be less than 18.5MPa 1/2 The case of (2) is denoted by "B".
In table 8, the column "SP value of the 1 st solvent < SP value of the 2 nd solvent" indicates the magnitude relation between the SP value of the 1 st solvent contained in the 1 st solution and the SP value of the 2 nd solvent contained in the 2 nd solution. Specifically, the case where the relation of the SP value of the 1 st solvent < the SP value of the 2 nd solvent is satisfied is denoted by "a", and the case where the relation is not satisfied is denoted by "B".
In Table 8, in the column "whether or not the 1 st solvent is contained as the additional solvent", the case where the 1 st solvents C-1 to C-3 are contained in the additional solvent is denoted by "A", and the case where the additional solvent is not contained is denoted by "B".
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Pattern formation and defect evaluation: EUV Exposure ]
[ Pattern formation and defect evaluation (3): EUV exposure and alkali aqueous development
AL412 (manufactured by Brewer Science Co.) was applied to a silicon wafer and baked at 205℃for 60 seconds, thereby forming a lower layer film having a film thickness of 30 nm. The resist compositions for EUV shown in Table 7 were applied thereon, and baked at 120℃for 60 seconds, thereby forming a photosensitive film having a film thickness of 30 nm.
The silicon wafer having the obtained resist film was subjected to pattern irradiation with respect to the photosensitive film using an EUV exposure apparatus (manufactured by Exitech Corporation, micro Exposure Tool, NA0.3, quadrupol, outer sigma 0.68, inner sigma 0.36). In addition, as a reticle (reticle), a mask having a line size=40 nm and a line-space=1:1 was used.
The exposed photosensitive film was baked (Post Exposure Bake (post bake); PEB) at 120 ℃ for 60 seconds, then developed with an aqueous tetramethylammonium hydroxide solution (TMAH, 2.38 mass%) for 30 seconds, followed by rinsing with pure water for 30 seconds. The silicon wafer was rotated at 4000rpm for 30 seconds and baked at 90℃for 60 seconds, whereby a line-space pattern with a pitch of 80nm and a line width of 40nm (space width of 40 nm) was obtained.
The obtained pattern wafer was inspected by using a defect evaluation device UVision5 manufactured by Applied Materials company, and a defect MAP was produced. Then, an image of the defect was obtained using semv ision G4 (manufactured by Applied Materials corporation), and the actual defect number of each silicon wafer was calculated. In addition, the actual defects generated in the pattern wafer are observed as images as shown in fig. 1 and 2, for example.
The actual defect number obtained was evaluated according to the following evaluation criteria. The smaller the number of defects, the better the result. The evaluation results are shown in table 9 below.
"S": the defect number is below 50
"A": the number of defects exceeds 50 and is less than 200
"B": the number of defects exceeds 200 and is 300 or less
"C": the number of defects exceeds 300 and is 400 or less
"D": the number of defects exceeds 400 and is less than 500
"E": the defect number exceeds 500
[ Pattern formation and defect evaluation (4): EUV exposure and organic solvent development
The development with butyl acetate as a developer for 30 seconds gave a line-space pattern with a pitch of 80nm and a line width of 40nm (space width of 40 nm), and the following procedure was followed (pattern formation and defect evaluation (3): EUV exposure and alkali aqueous solution development the pattern formation and defect number evaluation were carried out in the same manner. The evaluation results are shown in table 9 below.
Table 9 is shown below.
In table 9, in the column of "pattern formation method", the term (3) means alkali aqueous solution development, and the term (4) means organic solvent development.
TABLE 11
TABLE 9 Resist composition Pattern forming method Defects(s)
Example 21 Re-25 (3) A
Example 22 Re-26 (3) S
Example 23 Re-27 (3) D
Example 24 Re-28 (3) D
Example 25 Re-29 (3) A
Example 26 Re-30 (3) S
Example 27 Re-31 (3) S
Example 28 Re-32 (4) S
Example 29 Re-33 (4) D
Example 30 Re-34 (3) C
Example 31 Re-35 (3) B
Example 32 Re-36 (4) C
Example 33 Re-37 (4) B
Comparative example 5 Re-38 (3) E
Comparative example 6 Re-39 (3) E
Comparative example 7 Re-40 (4) E
Comparative example 8 Re-41 (4) E
As is clear from the results in table 9, according to the manufacturing method of the example, defects are suppressed. On the other hand, in the production method of the comparative example, it is found that the defect suppression property does not satisfy the desired requirement.
As is clear from the results of table 9, when the production method of the present invention satisfies the following condition T1 (preferably the following condition T2, more preferably the following condition T3), defects are further suppressed.
Condition T1: the manufacturing method of the present invention includes a step a, a step B2', a step B3, and a step C2 described below.
Step A: process for producing 1 st solution containing acid-decomposable resin and 1 st solvent
Procedure B2': a step of preparing a 2 nd solution containing a specific photoacid generator and a 2 nd solvent having a higher SP value than the 1 st solvent
And step B3: a step of mixing the 1 st solution and the 2 nd solution
Step C2: a step of further mixing the solution obtained in the step B3 (solution 3) with other components blended in the resist composition
Condition T2: the manufacturing method of the present invention includes steps a', B2", B3 and C2 described below.
Procedure a': preparation of acid-decomposable resinSP value is less than 18.5MPa 1/2 1 st solvent 1 st solution step
Procedure B2": preparation of a composition comprising the specified photoacid generator and having an SP value of 18.5MPa 1/2 The step of the 2 nd solution of the 2 nd solvent
And step B3: a step of mixing the 1 st solution and the 2 nd solution
Step C2: a step of further mixing the solution obtained in the step B3 (solution 3) with other components blended in the resist composition
Condition T3: the production method of the present invention includes a step A '", a step B2", a step B3, and a step C3' described below.
Procedure a' ": preparation of an acid-decomposable resin and an SP value of less than 18.5MPa 1/2 1 st solvent of (2), and a solid content concentration of 5.0 to 20.0 mass%
Procedure B2": preparation of a composition comprising the specified photoacid generator and having an SP value of 18.5MPa 1/2 The step of the 2 nd solution of the 2 nd solvent
And step B3: a step of mixing the 1 st solution and the 2 nd solution
Procedure C3': a step of further mixing the 1 st solvent and other components blended in the resist composition with the solution (3 rd solution) obtained through the step B3
In addition, the resist compositions Re-25-1 to Re-41-1 were prepared in the same manner as the respective preparation methods of the resist compositions Re-25 to Re-41 except that the acid diffusion control agent N-1 as a monovalent salt was used instead of the photoacid generator B as a polyvalent salt, and as a result, in the cases of the preparation methods 1 to 3 and the preparation methods 4 to 5, almost no difference in the defect suppression ability of the formed pattern was observed. When the acid diffusion control agent N-2, N-3 or N-4 was used in place of the acid diffusion control agent N-1, almost no difference in the defect suppressing ability of the formed pattern was observed between the cases of the preparation methods 1 to 3 and the preparation methods 4 to 5.

Claims (5)

1. A method for producing a actinic-ray-or radiation-sensitive resin composition, the composition comprising at least:
resins which are decomposed by the action of an acid to increase in polarity;
a compound that generates an acid by irradiation with actinic rays or radiation; and
The solvent is used for the preparation of the aqueous solution,
in the method for producing the actinic-ray-or radiation-sensitive resin composition,
the compound which generates an acid by irradiation with actinic rays or radiation contains 1 or more compounds selected from the group consisting of the following compounds (I) to (III),
mixing a 1 st solution containing the resin having increased polarity by decomposition by the action of an acid and a 1 st solvent with a 2 nd solution containing a solvent having a SP value greater than that of the 1 st solvent and a SP value of 18.5MPa to produce a actinic radiation-or radiation-sensitive resin composition 1/2 The above solvent 2 is 1 or more compounds selected from the group consisting of the above compounds (I) to (III),
wherein the compound (I) is a compound represented by the following general formula (Ia),
M 11 + A 11 - -L 1 -A 12 - M 12 + (Ia)
in the general formula (Ia), M 11 + M and M 12 + Independently of each other, represent an organic cation, A 11 - A is a 12 - Each independently represents an anionic functional group, wherein A 12 - Representation and representation of A 11 - Represented by different structures of anionic functional groups, L 1 Represents a linking group of valence 2,
the compound represented by the general formula (Ia) is produced by HA by irradiation with actinic rays or radiation 11 -L 1 -A 12 An acid represented by H is used as a base,
in the general formula (Ia), M is as follows 11 + M and M 12 + Represented organic cations are replaced by H + The compound PIa is HA 11 -L 1 -A 12 H is derived from A 12 The acid dissociation constant a2 of the acid site represented by H is larger than that derived from HA 11 The acid dissociation constant a1 of the acid site,
the compound (II) is a compound represented by the following general formula (IIa),
in the general formula (IIa), M 21 + M and M 22 + Independently of each other, represent an organic cation, A 21 - A is a 22 - Each independently represents an anionic functional group, wherein A 22 -representing and consisting of a 21 - Represented by different structures of anionic functional groups, L 2 An organic group having a valence of (n1+n2), n1 represents an integer of 2 or more, n2 represents an integer of 1 or more,
the compound represented by the general formula (IIa) generates an acid represented by the following general formula (IIa-1) by irradiation with actinic rays or radiation,
in the general formula (IIa), the compound represented by M 21 + M and M 22 + Represented organic cations are replaced by H + The compound PIIa represented by the general formula (IIa-1) is derived from A 22 The acid dissociation constant a2 of the acid site represented by H is larger than that derived from HA 21 The acid dissociation constant a1 of the acid site,
in the general formula (IIa), M 21 + 、M 22 + 、A 21 - A is a 22 - Respectively with M in the general formula (Ia) 11 + 、M 12 + 、A 11 - A is a 12 - The meaning of (c) is the same,
in the general formula (IIa), n 1M 21 + Each other, n 1A 21 + Each of which represents a group identical to each other,
the compound (III) is a compound represented by the following general formula (IIIa),
in the general formula (IIIa), M 31 + Represents an organic cation, A 31 - Represents an anionic functional group, L 3 L and L 4 Each independently represents a 2-valent linking group, R 2X A substituent of 1-valent bond is represented,
the compound represented by the general formula (IIIa) is produced by irradiation of actinic rays or radiation 31 -L 3 -N(R 2X )-L 4 -A 31 An acid represented by H is used as a base,
in the general formula (IIIa), M 31 + A is a 31 - Respectively with M in the general formula (Ia) 11 + A is a 11 - The meaning of (c) is the same,
in the general formula (IIIa), L 3 L and L 4 Respectively with L in the general formula (Ia) 1 The meaning of (c) is the same,
in the general formula (IIIa), 2M 31 + Each other and 2A 31 - Each of which represents the same group as each other.
2. The method for producing a actinic-ray-or radiation-sensitive resin composition according to claim 1, wherein,
The SP value of the 1 st solvent is less than 18.5MPa 1/2 。
3. The method for producing a actinic-ray-or radiation-sensitive resin composition according to claim 1, wherein,
the concentration of the solid content of the 1 st solution is 5.0 to 20.0 mass%,
the 1 st solvent is further mixed in the 3 rd solution obtained by mixing the 1 st solution with the 2 nd solution to produce a actinic-ray-or radiation-sensitive resin composition.
4. A pattern forming method includes the steps of:
a step of forming a resist film on a support using the actinic-ray-or radiation-sensitive resin composition obtained by the process for producing an actinic-ray-or radiation-sensitive resin composition according to any one of claims 1 to 3;
exposing the resist film; and
and developing the exposed resist film with a developer.
5. A manufacturing method of an electronic device, comprising the pattern forming method of claim 4.
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